Coordination catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation

ABSTRACT

The present invention is directed to a coordinating catalyst system comprising at least one bidentate or tridentate ligand containing pre-catalyst transition metal compound, (e.g., 2,6-bis (2,4,6-trimethylarylamino)pyridyl iron dichloride), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology.

FIELD OF THE INVENTION

The invention relates to coordination catalyst systems, which comprise asupport-activator in agglomerate form and a coordination catalystcomponent and methods of their preparation.

BACKGROUND OF THE INVENTION

Coordination catalyst systems, which are usually based on transitionmetal compounds of Groups 3 to 10 and organometallic compounds of Group13 of the Periodic Table of the Elements, are exceptionally diversecatalysts which are employed in chemical reactions of and witholefinically unsaturated compounds. Such reactions are embodied inprocesses for the preparation of olefin polymers by coordinationpolymerization.

The preparation of polyethylene of increased density (high-densitypolyethylene, HDPE) and of polymers and copolymers of ethylene,propylene or other 1-alkenes is of considerable industrial importance.

The prevailing belief on the reaction mechanism of coordinationcatalysts is that a transition metal compound forms a catalyticallyactive center to which the olefinically unsaturated compound bonds bycoordination in a first step. Olefin polymerization takes place viacoordination of the monomers and a subsequent insertion reaction into atransition metal-carbon or a transition metal-hydrogen bond.

The presence of organometallic compounds (e.g., organoaluminum compoundssuch as methylalumoxane) in the coordination catalyst systems or duringthe catalyzed reaction is thought to be necessary in order to activatethe catalyst, or maintain its activity, by reduction and, whereappropriate, alkylation or formation of a complex system. Thesecompounds were therefore also called cocatalysts. The compoundcontaining the transition metal atom, which is eventually activated, istypically called the pre-catalyst and after activation, the primarycatalyst.

The best known industrially used catalyst systems for coordinationpolymerization are those of the “Ziegler-Natta catalyst” type and the“Phillips catalyst” type. The former comprise the reaction product of ametal alkyl or hydride of elements of the first three main groups of thePeriodic Table and a reducible compound of a transition metal element ofGroups 4 to 7 the combination used most frequently comprising analuminum alkyl, such as diethylaluminum chloride, and titanium (IV)chloride. More recent highly active Ziegler-Natta catalysts are systemsin which the titanium compound is fixed chemically to the surface ofmagnesium compounds, such as, in particular, magnesium chloride.

More recent developments have focused on single-site catalyst systems.Such systems are characterized by the fact that their metal centersbehave alike during polymerization thus making very uniform polymers.

Catalysts are judged to behave in a single-site manner when the polymerthey make meets some basic criteria (e.g., narrow molecular weightdistribution, or uniform comonomer distribution). Thus, the metal canhave any ligand set around it and be classified as “single-site” as longas the polymer that it produces has certain properties.

Includable within single-site catalyst systems are metallocene catalystsand constrained geometry catalysts.

A “metallocene” is conventionally understood to mean a metal (e.g., Zr,Ti, Hf, Sc, Y, Vi or La) complex that is bound to two cyclopentadienyl(Cp) rings, or derivatives thereof, such as indenyl, tetrahydroindenyl,fluorenyl and mixtures. In addition to the two Cp ligands, other groupscan be attached to the metal center, most commonly halides and alkyls.The Cp rings can be linked together (so-called “bridged metallocene”structure), as in most polypropylene catalysts, or they can beindependent and freely rotating, as in most (but not all)metallocene-based polyethylene catalysts. The defining feature is thepresence of two Cp ligands or derivatives.

Metallocene catalysts can be employed either as so-called “neutralmetallocenes” in which case an alumoxane, such as methylalumoxane, isused as a co-catalyst, or they can be employed as so-called “cationicmetallocenes” which incorporate a stable and loosely boundnon-coordinating anion as a counter ion to a cationic metal metallocenecenter. Cationic metallocenes are disclosed in U.S. Pat. Nos. 5,064,802;5,225,500; 5,243,002; 5,321,106; 5,427,991; and 5,643,847; and EP 426637 and EP 426 638.

“Constrained geometry” is a term that refers to a particular class oforganometallic complexes in which the metal center is bound by only onemodified Cp ring or derivative. The Cp ring is modified by bridging to aheteroatom such as nitrogen, phosphorus, oxygen, or sulfur, and thisheteroatom also binds to the metal site. The bridged structure forms afairly rigid system, thus the term “constrained geometry”. By virtue ofits open structure, the constrained geometry catalyst can produce resins(long chain branching) that are not possible with normal metallocenecatalysts.

Still more recently, late transitional metal (e.g., Fe, Co, Ni, or Pd)bidentate and tridentate catalyst systems have been developed.Representative disclosures of such late transition metal catalysts arefound in U.S. Pat. No. 5,880,241 and its divisional counterparts U.S.Pat. Nos. 5,880,323; 5,866,663; 5,886,224; and 5,891,963, and PCTInternational Application Nos. PCT/US98/00316; PCT/US97/23556;PCT/GB99/00714; PCT/GB99/00715; and PCT/GB99/00716.

Both the single site and late transition metal pre-catalysts typicallyrequire activation to form a cationic metal center by an organometalLewis acid (e.g., methyl alumoxane (MAO)) (characterized as operatingthrough a hydrocarbyl abstraction mechanism). Such activators orcocatalysts are pyrophoric (or require pyrophoric reagents to make thesame), and are typically employed in quantities which are multiples ofthe catalyst. Attempts to avoid such disadvantages have led to thedevelopment of borane (e.g., trispentaflurophenylborane) and borate(e.g., ammonium tetrakispentaflurophenylborate) activators which arenon-pyrophoric but more expensive to manufacture. These factorscomplicate the development of heterogeneous versions of such catalystsystems in terms of meeting cost and performance targets.

Use of these catalysts and related types in various polymerizationprocesses can give products with sometimes extremely differentproperties. In the case of olefin polymers, which are generally known tobe important as materials, the suitability for particular applicationsdepends, on the one hand, on the nature of the monomers on which theyare based and on the choice and ratio of comonomers and the typicalphysical parameters which characterize the polymer, such as averagemolecular weight, molecular weight distribution, degree of branching,degree of crosslinking, crystallinity, density, presence of functionalgroups in the polymer and the like, and on the other hand, on propertiesresulting from the process, such as content of low molecular weightimpurities and presence of catalyst residues, and last but not least oncosts.

In addition to realization of the desired product properties, otherfactors are decisive for evaluating the efficiency of a coordinationcatalyst system, such as the activity of the catalyst system, that is tosay the amount of catalyst required for economic conversion of a givenamount of olefin, the product conversion per unit time and the productyield. Catalyst systems such as the Fe or Co catalysts described herein,which exhibit high productivity and high specificity in favor of a lowdegree of branching of the polymer, are sought for certain applications.Catalyst systems utilizing the Ni and Pd catalysts described herein seekto achieve highly branched polymers with reasonable productivity.

The stability and ease of handling of the catalyst or its components isanother factor which affects the choice of commercial embodimentsthereof. Practically all known coordination catalysts are extremelysensitive to air and moisture to varying degrees. Coordination catalystsare typically reduced in their activity or irreversibly destroyed byaccess to (atmospheric) oxygen and/or water. Most Ziegler-Natta andmetallocene catalysts, for example, deactivate spontaneously on accessto air and become unusable. Most coordination catalysts must thereforetypically be protected from access of air and moisture duringpreparation, storage and use, which of course makes handling difficultand increases the expenditure required. The bi-end tri-dentate catalystsdescribed herein are known to be more tolerant toward oxygen.

A still further factor to be considered is the ability to utilize thecoordination catalyst as a heterogeneous catalyst system. The advantagesof a heterogeneous catalyst system are more fully realized in a slurrypolymerization process. More specifically, slurry polymerizations areoften conducted in a reactor wherein monomer, catalysts, and diluent arecontinuously fed into the reactor. The solid polymer that is produced isnot dissolved in the diluent and is allowed to settle out before beingperiodically withdrawn form the reactor. In this kind of polymerization,factors other than activity and selectivity, which are always present insolution processes, become of paramount importance.

For example, in the slurry process it is desired to have a supportedcatalyst which produces relatively high bulk density polymer. If thebulk density is too low, the handling of the solid polymer becomesimpractical. It is also an advantage to have the polymer formed asuniform, spherical particles that are relatively free of fines. Althoughfines can have a high bulk density, they also do not settle as well aslarger particles and they present additional handling problems with thelater processing of the polymer fluff.

Furthermore, slurry polymerization processes differ in other fundamentalways from the typical solution polymerization processes. The latterrequires higher reaction temperatures (>130° C.) and pressures (>450psi) and often results in lower molecular weight polymers. The lowermolecular weight is attributed to the rapid chain-termination ratesunder such reaction conditions. Although lowering the reactiontemperature and/or pressure, or changing molecular structure of themetallocene catalyst can produce higher molecular weight polymer in asolution process, it becomes impractical to process the resulting highmolecular weight polymers in the downstream equipment due to the highviscosity.

In contrast, a slurry reaction process overcomes many of the abovedisadvantages by simply operating at lower temperature (<100° C.). As aresult, a higher molecular weight polymer with a uniform particle sizeand morphology can be routinely obtained. It is also advantageous tocarry out slurry reactions with sufficiently high polymerizationefficiencies such that residues from the polymerization catalysts do nothave to be removed from the resulting polymers. The above-discussedadvantages of slurry polymerization processes provides incentive fordeveloping coordination catalysts in heterogeneous form. Thus far, gasphase polymerization processes are only practical with a heterogeneouscatalyst system

Finally, evaluation of a coordination catalyst system must includeprocess considerations which influence the morphology (e.g., bulkdensity) of the resulting polymer, the environmental friendliness of theprocess, and avoidance of reactor fouling.

Thus, there has been a continuing search to develop a coordinationcatalyst system, preferably a heterogeneous coordination catalystsystem, which demonstrates high catalyst activity, is free of reactorfouling, produces polymer products having good resin morphology whilesimultaneously being very process friendly (e.g., easy to make) andinexpensive to make.

There has also been a particular need to discover compounds which areless sensitive to deactivation and/or less hazardous and still suitableas activating components in coordination catalyst systems.

The present invention was developed in response to these searches.

International application No. PCT/US97/11953 (International PublicationNo. WO 97/48743) is directed to frangible, spray dried agglomeratecatalyst supports of silica gel, which possess a controlled morphologyof microspheroidal shape, rough scabrous appearance, and interstitialvoid spaces which penetrate the agglomerate surface and are ofsubstantially uniform size and distribution. The agglomerates alsopossess a 1-250 micron particle size, 1-1000 m²/g surface area, and anAttrition Quality Index (AQI) of at least 10. The agglomerates arederived from a mixture of dry milled inorganic oxide particles, e.g.,silica gel and optionally but preferably wet milled inorganic oxideparticles, e.g., silica gel particles (which preferably contain acolloidal content of less than 1 micron particle), slurried in water forspray drying. The high AQI assures that the agglomerates are frangibleand that the polymerization performance is improved. The controlledmorphology is believed to permit the constituent particles of theagglomerates to be more uniformly impregnated or coated withconventional olefin polymerization catalysts. Clay is not disclosed assuitable metal oxide.

U.S. Pat. No. 5,633,419 discloses the use of spray dried silica gelagglomerates as supports for Ziegler-Natta catalyst systems.

U.S. Pat. No. 5,395,808 discloses bodies made by preparing a mixture ofultimate particles of bound clay, with one or more optional ingredientssuch as inorganic binders, extrusion or forming aids, burnout agents orforming liquid, such as water. Preferably the ultimate particles areformed by spray drying. Suitable binders include silica when Kaolin clayis used as the inorganic oxide. The bodies are made from the ultimateparticles and useful methods for forming the bodies include extrusion,pelletization, balling, and granulating. Porosity is introduced into thebodies during their assembly from the ultimate particles, and resultsprimarily from spaces between the starting particles. The porous bodiesare disclosed to be useful as catalyst supports. See also U.S. Pat. Nos.5,569,634; 5,403,799; and 5,403,809; and EP 490 226 for similardisclosures.

U.S. Pat. No. 5,362,825 discloses olefin polymerization catalystsproduced by contacting a pillared clay with a Ziegler-Natta catalyst,i.e., a soluble complex produced from the mixture of a metal dihalidewith at least one transition metal compound in the presence of a liquiddiluent. The resulting mixture is in turn contacted with anorganoaluminum halide to produce the catalyst.

U.S. Pat. No. 5,807,800 is directed to a supported metallocene catalystcomprising a particulate catalyst support, such as a molecular sievezeolite, and a stereospecific metallocene, supported on the particulatesupport and incorporating a metallocene ligand structure having twosterically dissimilar cyclopentadienyl ring structures coordinated witha central transition metal atom. At column 4 of the backgrounddiscussion, it is disclosed that cationic metallocenes which incorporatea stable non-coordinating anion normally do not require the use ofalumoxane.

U.S. Pat. No. 5,238,892 discloses the use of undehydrated silica as asupport for metallocene and trialkylaluminum compounds.

U.S. Pat. No. 5,308,811 discloses an olefin polymerization catalystobtained by contacting (a) a metallocene-type transition metal compound,(b) at least one member selected from the group consisting of clay, clayminerals, ion exchanging layered compounds, diatomaceous earth,silicates and zeolites, and (c) an organoaluminum compound. Component(b) may be subjected to chemical treatment, which, for example, utilizesion exchangeability to substitute interlaminar exchangeable ions of theclay with other large bulky ions to obtain a layered substance havingthe interlaminar distance enlarged. Such bulky ions play the role ofpillars, supporting the layered structure, and are therefore calledpillars. Guest compounds, which can be intercalated, include cationicinorganic compounds derived from such materials as titaniumtetrachloride and zirconium tetrachloride. SiO₂ may be present duringsuch intercalation of guest compounds. The preferred clay ismontmorillonite. Silica gel is not disclosed as a suitable component(b).

U.S. Pat. No. 5,753,577 discloses a polymerization catalyst comprising ametallocene compound, a co-catalyst such as proton acids, ionizedcompounds, Lewis acids and Lewis acidic compounds, as well as claymineral. The clay can be modified by treatment with acid or alkali toremove impurities from the mineral and possibly to elute part of themetallic cations from the crystalline structure of the clay. Examples ofacids which can effect such modification include Bronsted acids such ashydrochloric, sulfuric, nitric and acetic acids. The preferredmodification of the clay is accomplished by exchanging metallic ionsoriginally present in the clay with specific organic cations such asaliphatic ammonium cations, oxonium ions, and onium compounds such asaliphatic amine hydrochloride salts. Such polymerization catalysts mayoptionally be supported by fine particles of SiO₂, Al₂O₃, ZrO₂, B₂O₃,CaO, ZnO, MgCl₂, CaCl₂, and mixtures thereof. (Col. 3, line 48; Col. 21,line 10 et seq.). The fine particle support may be of any shapepreferably having a particle size in the range of 5-200 microns, andpore size ranges of from 20-100 Å. Use of metal oxide support is notdescribed in the examples.

U.S. Pat. No. 5,399,636 discloses a composition comprising a bridgedmetallocene which is chemically bonded to an inorganic moiety such asclay or silica. Silica is illustrated in the working examples as asuitable support, but not clay.

EP 849 292 discloses an olefin polymerization catalyst consistingessentially of a metallocene compound, a modified clay compound, and anorganoaluminum compound. The modification of the clay is accomplished byreaction with specific amine salts such as a proton acid salt obtainedby the reaction of an amine with a proton acid (hydrochloric acid). Thespecifically disclosed proton acid amine salt is hexylaminehydrochloride. The modification of the clay results in exchange of theammonium cation component of the proton acid amine salt with the cationsoriginally present in the clay to form the mineral/organic ion complex.

U.S. Pat. No. 5,807,938 discloses an olefin polymerization catalystobtained by contacting a metallocene compound, an organometalliccompound, and a solid catalyst component comprising a carrier and anionized ionic compound capable of forming a stable anion on reactionwith the metallocene compound. Suitable carriers disclosed includeinorganic compounds or organic polymeric compounds. The inorganiccompounds include inorganic oxides, such as alumina, silica,silica-alumina, silica magnesia; clay minerals; and inorganic halides.The ionized ionic compound contains an anionic component and a cationiccomponent. The cationic component preferably comprises a Lewis Basefunctional group containing an element of the Group 15 or 16 of thePeriodic Table such as ammonium, oxionium, sulfonium, and phosphonium,cations. The cation component may also contain a functional group otherthan Lewis Base function groups, such as carbonium, tropinium, and ametal cation. The anion component includes those containing a boron,aluminum, phosphorous or antimony atom, such as an organoboron,organoaluminum, organophosphorous, and organoantimony anions. Thecationic component is fixed on the surface of the carrier. Only silicaor chlorinated silica are employed in the working examples as a carrier.In many examples, the silica surface is modified with a silane.

U.S. Pat. No. 5,830,820 discloses an olefin polymerization catalystcomprising a modified clay mineral, a metallocene compound, and anorganoaluminum compound. The clay mineral is modified with a compoundcapable of introducing a cation into the layer interspaces of the claymineral. Suitable cations which are inserted into the clay include thosesaving a proton, namely, Bronsted acids such trimethylammonium, as wellas carbonium ions, oxonium ions, and sulfonium ions. Representativeanions include chlorine ion, bromide ion, and iodide ion.

EP 881 232 is similar to U.S. Pat. No. 5,830,820, except that theaverage particle size of the clay is disclosed as being less than 10microns.

EP 849 288 discloses an olefin polymerization catalyst consistingessentially of a metallocene compound, an organoaluminum compound, and amodified clay compound. The clay is modified by contact with a protonacid salt of certain specific amine compounds, such as hexylaminechloride.

JP Kokai Patent HEI 10-338516 discloses a method for producing ametallic oxide intercalated in a clay mineral which comprises swellingand diluting the clay mineral, having a laminar structure, with water toform a sol; adding an organometallic compound to an aqueous solutioncontaining organic acid to form a sol that contains the metalliccompound; mixing the swelling clay mineral sol with the metalliccompound containing sol and agitating to intercalate the metalliccompound between the layers in the swollen clay mineral; and washing,dehydrating, drying and roasting the clay mineral that has the metalliccompound intercalated therein. Suitable metallic oxides include those oftitanium, zinc, iron, and tin.

U.S. Pat. No. 4,981,825 is directed to a dried solid compositioncomprising clay particles and inorganic metal oxide particlessubstantially segregated from the clay particles. More specifically, themetal oxide particles are sol particles which tend to fuse uponsintering. Consequently, by segregating the sol particles withsmectite-type clay particles, fusion of the sol particles is reducedunder sintering conditions thereby preventing a loss of surface area.The preferred metal oxide is colloidal silica having an average particlesize between 40 and 800 angstroms (0.004 and 0.08 microns), preferably40 and 80 angstroms. The ratio of the metal oxide to clay is betweenabout 1:1 to 20:1, preferably 4:1 to 10:1. The end product is describedat Column 3, line 50 et seq. as sol particle-clay composites in whichthe clay platelets inhibit aggregation of the sol particles. Suchproducts are made up entirely of irregular sol-clay networks in whichthe clay platelets are placed between the sol particles. The result is acomposite with very high surface area, and ability to retain such highsurface area at elevated temperatures. This arrangement is alsodistinguished from intercalation of the clay by the silica. The subjectcompositions are disclosed in the abstract to be useful for catalyticgaseous reactions and removal of impurities from gas streams. Specificcatalysts systems are not disclosed.

U.S. Pat. No. 4,761,391 discloses delaminated clays whose x-raydefraction patterns do not contain a distinct first order reflection.Such clays are made by reacting synthetic or natural swelling clays witha pillaring agent selected from the group consisting of polyoxymetalcations, mixtures of polyoxymetal cations, colloidal particlescomprising alumina, silica, titania, chromia, tin oxide, antimony oxideor mixtures thereof, and cationic metal clusters comprising nickel,molybdenum, cobalt, or tungsten. The resulting reaction product is driedin a gaseous medium, preferable by spray drying. The resulting acidicdelaminated clays may be used as the active component of cracking andhydroprocessing catalysts. The ratio of clay to pillaring agent isdisclosed to be between about 0.1 and about 10. To obtain the delminatedclay, a suspension of swelling clay, having the proper morphology, e.g.,colloidal particle size, is mixed with a solution or a suspension of thepillaring agent at the aforedescribed ratios. As the reactants aremixed, the platelets of clay rapidly sorb the pillaring agent producinga flocculated mass comprised of randomly oriented pillared plateletaggregates. The flocculated reaction product or gel is then separatedfrom any remaining liquid by techniques such as centrifugationfiltration and the like. The gel is then washed in warm water to removeexcess reactants and then preferably spray dried. The pillaring agentupon heating is converted to metal oxide clusters which prop apart theplatelets of the clay and impart the acidity which is responsible forthe catalytic activity of the resultant delaminated clay. The x-raydefraction pattern of such materials contains no distinct first order ofreflection which is indicative of platelets randomly oriented in thesense that, in addition to face-to-face linkages of platelets, there arealso face-to-edge and edge-to-edge linkages. The utilities described atColumn 8, Lines 55 et seq. include use as components of catalyst,particularly hydrocarbon conversion catalysts, and most preferably ascomponents of cracking and hydrocracking catalysts. This stems from thefact that the because the clay contains macropores as well asmicropores, large molecules that normally cannot enter the pores ofzeolites will have access to the acid sites in the delaminated claysmaking such materials more efficient in cracking of high molecularweight hydrocarbon constituents. (See also U.S. Pat. No. 5,360,775.)

U.S. Pat. No. 4,375,406 discloses compositions containing fibrous claysand precalcined oxides prepared by forming a fluid suspension of theclay with the precalcined oxide particles, agitating the suspension toform a co-dispersion, and shaping and drying the co-dispersion. Suitablefibrous clays include aluminosilicates, magnesium silicates, andaluminomagnesium silicates. Examples of suitable fibrous clays areattapulgite, playgorskite, sepiolite, haloysite, endellite, chrysotileasbestos, and imogolite. Suitable oxides include silica. The ratio offibrous clay to precalcined oxide is disclosed to vary from 20:1 to 1:5by weight. In contrast, the presently claimed invention does not employfibrous clays but does not exclude their presence.

Additional patents which disclose intercalated clays are U.S. Pat. Nos.4,629,712 and 4,637,992. Additional patents which disclose pillaredclays include U.S. Pat. Nos. 4,995,964 and 5,250,277.

A paper presented at the MetCon '99 Polymers in Transition Conference inHouston, Tex., on Jun. 9-10, 1999, entitled “Novel ClayMineral-Supported Metallocene Catalysts for Olefin Polymerization” byYoshinor Suga, Eiji Isobe, Toru Suzuki, Kiyotoshi Fujioka, TakashiFujita, Yoshiyuki Ishihama, Takehiro Sagae, Shigeo Go, and Yumito Ueharadiscloses olefin polymerization catalysts comprising metallocenecompounds supported on dehydrated clay minerals optionally in thepresence of organoaluminum compounds. At page 5 it is disclosed thatcatalysts prepared with fine clay mineral particles has had operationaldifficulties such as fouling which make them unsuitable for slurry andgas phase processes. Thus, a granulation method was developed to givethe clay minerals a uniform spherical shape. The method for producingthis spherical shape is not disclosed.

PCT International Application No. PCT/US96/17140, corresponding to U.S.Ser. No. 562,922, discloses a support for metallocene olefinpolymerizations comprising the reaction product of an inorganic oxidecomprising a solid matrix having reactive hydroxyl groups or reactivesilane functionalized derivatives of hydroxyl groups on the surfacethereof, and an activator compound. The activator compound comprises acation which is capable of reacting with the metallocene compound toform a catalytically active transition metal complex and a compatibleanion containing at least one substituent able to react with theinorganic oxide matrix through residual hydroxyl functionalities orthrough the reactive silane moiety on the surface thereof. Therepresentative example of a suitable anion activator is tris(pentafluorophenyl)(4-hydroxyphenyl)borate. Suitable inorganic oxidesdisclosed include silica, alumina, and aluminosilicates.

U.S. Pat. No. 5,880,241 discloses various late transition metalbidentate catalyst compositions. At column 52, lines 18 et seq., it isdisclosed that the catalyst can be heterogenized through a variety ofmeans including the use of heterogeneous inorganic materials asnon-coordinating counter ions. Suitable inorganic materials disclosedinclude aluminas, silicas, silica/aluminas, cordierites, clays, andMgCl₂ but mixtures are not disclosed. Spray drying the catalyst with itsassociated non-coordinating anion onto a polymeric support is alsocontemplated. Examples 433 and 434 employ montmorillonite clay as asupport but polymer morphology is not disclosed for these examples.

PCT International Application No. PCT/US97/23556 discloses a process forpolymerizing ethylene by contact with Fe or Co tridentate ionic complexformed either through alkylation or abstraction of the metal alkyl by astrong Lewis acid compound, e.g., MAO, or by alkylation with a weakLewis acid, e.g., triethylaluminum and, subsequent abstraction of theresulting alkyl group on the metal center with a stronger Lewis acid,e.g., B(C₆F₅)₃. The Fe or Co tridentate compound may be supported bysilica or alumina and activated with a Lewis or Bronsted acid such as analkyl aluminum compound (pg. 19, line 1 et seq.). Acidic clay (e.g.,montmorillonite) may function as the support and replace the Lewis orBronsted acid. Examples 43-45 use silica supported MAO, and Example 56employs dehydrated silica as a support for the Co complex. Polymermorphology is not discussed.

PCT International Application No. PCT/US98/00316 discloses a process forpolymerizing propylene using catalysts similar to the above discussedPCT-23556 application.

U.S. Ser. No. 09/166,545, filed Oct. 5, 1998, by Keng-Yu Shih, aninventor of the present application, discloses a supported latetransition metal bidentate or tridentate catalyst system containinganion and cation components wherein the anion component contains boron,aluminum, gallium, indium, tellurium and mixtures thereof covalentlybonded to an inorganic support (e.g. SiO₂) through silane derivedintermediates such as a silica-tethered anilinium borate.

U.S. Ser. No. 09/431,803 filed on an even date herewith by Keng-Yu Shihdiscloses the use of silica agglomerates as a support for transitionmetal catalyst systems employing specifically controlled (e.g., verylow) amounts of non-abstracting aluminum alkyl activators.

SUMMARY OF THE INVENTION

The present invention relies on the discovery that certain agglomeratecomposite particles of an inorganic oxide (e.g., silica) and an ionexchanging layered compound (e.g., clay) are believed to possessenhanced Lewis acidity dispersion and accessibility which renders themextremely proficient support-activators for certain non-metallocene andnon-constrained geometry bi- and tridentate containing transition metalcompound pre-catalysts. More specifically, it is believed that theagglomerate particles incorporate the ionizable clay particles in such away that their known Lewis acidity is more uniformly dispersedthroughout the particle while simultaneously being made more accessiblefor interaction with the pre-catalyst. It is believed that this permitsthe support-activator to effectively and simultaneously activate, e.g.,ionize, the pre-catalyst when in a pre-activated (e.g., ionizable) stateas well as support the active catalyst during polymerization. Thiseliminates the need to use additional ionizing agents which areexpensive, and introduce added complexity to the system. In contrast,the support-activator is inexpensive, environmentally friendly, and easyto manufacture.

The present invention relies on the further discovery thatpre-activation of the pre-catalyst is very sensitive to the level ofcertain organometallic compounds and is induced by extremely low amountsof the same. This further reduces the catalyst system costs, andeliminates the need for expensive MAO or borate activators of the priorart while simultaneously achieving extremely high activity.

A still further aspect of the discovery of the present invention is thatthe support-activator apparently immobilizes the pre-catalyst byadsorption and/or absorption, preferably by chemadsorption and/orchemabsorption from a slurry of the same without any specialimpregnation steps, which slurry can actually be used directly for theslurry polymerization of olefins. The resulting polymer morphology isindicative of a heterogeneous polymerization which is consistent withthe observation (based on x-ray powder diffraction, cross-sectionmicroprobe elemental analysis and the color induced in thesupport-activator) that the support-activator is readily impregnated bythe pre-catalyst such that it is believed to react with the same.Moreover, the microspheroidal morphology of the catalyst system coupledwith the immobilization of the active catalyst therein is believed tocontribute to the extremely desirable observed polymer morphologybecause it prevents reactor fouling, eliminates polymer fines andexhibits a high bulk density. The catalyst system can be employed as aslurry or dry powder.

A still even further aspect of the discovery of the present invention isthe functional interrelationship which exists between the inorganicoxide: layered material weight ratio, the calcination temperature, andthe amount of organoaluminum compound on the one hand, and the catalystactivity on the other hand, such that these variables can be controlledto exceed the activity of the same pre-catalyst supported and/oractivated by the inorganic oxide alone, or the layered material (e.g.,clay) alone, while simultaneously producing good polymer morphology.

Accordingly, in one aspect of the invention there is provided acoordinating catalyst system, preferably a heterogeneous coordinatingcatalyst system, capable of polymerizing olefins comprising:

(I) as a pre-catalyst, at least one non-metallocene, non-constrainedgeometry, bidentate transition metal compound or tridentate transitionmetal compound capable of (A) being activated upon contact with thesupport-activator, or (B) being converted, upon contact with anorganometallic compound, to an intermediate capable of being activatedupon contact with the support-activator, wherein the transition metal isat least one member selected from Groups 3 to 10 of the Periodic table;in intimate contact with

(II) support-activator agglomerate comprising a composite of (A) atleast one inorganic oxide component selected from SiO₂, Al₂O₃, MgO,AlPO₄,TiO₂, ZrO₂, Cr₂O₃ and (B) at least one ion containing layeredmaterial having interspaces between the layers and sufficient Lewisacidity, when present within the support-activator, to activate thepre-catalyst when the pre-catalyst is in contact with thesupport-activator, said layered material having a cationic component andan anionic component, wherein said cationic component is present withinthe interspaces of the layered material, said layered material beingintimately associated with said inorganic oxide component within theagglomerate in an amount sufficient to improve the activity of thecoordinating catalyst system for the polymerization of ethylene monomer,expressed as Kg polyethylene/g of catalyst system/hour, relative to theactivity of a corresponding coordination catalyst system employing thesame pre-catalyst but in the absence of either component A (inorganicoxide) or B (layered material) of the support activator, wherein theamount of the pre-catalyst and support-activator which is in intimatecontact is sufficient to provide a ratio of micromoles of pre-catalystto grams of support-activator of from about 5:1 to about 500:1.

In another aspect of the present invention, there is provided a processfor making the above catalyst system which comprises:

(I) agglomerating to form a support-activator:

(A) at least one inorganic oxide component selected from SiO₂, Al₂O₃,MgO, AlPO₄, TiO₂, ZrO₂, Cr₂O₃ with

(B) at least one ion containing layered material having interspacesbetween the layers and sufficient Lewis acidity, when present within thesupport-activator, to activate the transition metal of the pre-catalystcompound of (II) when in contact with the support-activator, saidlayered material having a cationic component and an anionic component,wherein said cationic component is present within the interspaces of thelayered material, said layered material being intimately associated withsaid inorganic oxide component within said agglomerate in an amountsufficient to improve the activity of the coordinating catalyst systemfor the polymerization of ethylene monomer, expressed as Kg polyethyleneper gram of catalyst system per hour, relative to the activity of acorresponding coordination catalyst system employing the samepre-catalyst but in the absence of either component A or B of thesupport-activator;

(II) providing as a pre-catalyst at least one non-metallocene,non-constrained geometry pre-catalyst transition metal compound selectedfrom bidentate transition metal compound, and tridentate transitionmetal compound, capable of (A) being activated upon contact with thesupport-activator, or (B) being converted, upon contact with anorganometallic compound, to an intermediate capable of being activatedupon contact with the support-activator, wherein the transition metal isat least one member selected from Groups 3 to 10 of the Periodic Table;

(III) contacting the support-activator and pre-catalyst in the presenceof at least one inert liquid hydrocarbon in a manner sufficient toprovide in the liquid hydrocarbon, a ratio of micromoles of pre-catalystto grams of support-activator of from about 5:1 to about 500:1 and tocause at least one of absorption and adsorption of the pre-catalyst bythe support-activator.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a scanning electron micrograph of a cross-section of anagglomerate particle prepared in accordance with Example 1, Run No. 4.The photograph was taken with a scanning electron microscope andrepresents a 1000-fold magnification of the actual agglomerate particle.

FIG. 2 is a scanning electron micrograph of a cross-section of anagglomerate particle prepared in accordance with Example 1, Run No. 4.The photograph was taken with a scanning electron microscope andrepresents 2000-fold magnification of the actual agglomerate particle.

FIGS. 3 to 14 are contour maps of the activity (KgPE/g of catalystsystem per hour) of coordination catalyst systems prepared and tested inaccordance with Example 8. Each individual plot line of each Figure isassociated with a number which expresses the expected catalyst activityat the coordinate conditions of wt. % clay in the support-activator(based on the weight of silica+clay) (y-axis) and the millimoles oftriisobutyl aluminum per gram of support-activator (x-axis).

DESCRIPTION OF PREFERRED EMBODIMENTS

As indicated above, the present invention employs a non-metallocenenon-constrained geometry neutral transition metal compound as apre-catalyst which can be activated by contact with thesupport-activator and optionally an organometallic compound describedhereinafter. An activated transition metal compound is one (a) in whichthe central transition metal atom such as that, represented by Z in thefollowing formulas, is changed, such as by transforming into a state offull or partial positive charge, that is, the transition metal compoundbecomes a cation or cation-like, in its association with a stable anionor anion-like moiety and (b) that is capable of catalyzing thepolymerization of olefins under polymerization conditions.

More specifically, the transition metal pre-catalyst can be at least onebidentate transition metal compound, at least one tridentate transitionmetal compound or mixtures thereof capable of (A) being activated uponcontact with the support-activator or (B) being converted upon contactwith an organometallic compound, to an intermediate which is capable ofbeing activated upon contact with the support-activator.

The bidentate pre-catalyst compounds can be generically represented bythe formula:

and the tridentate pre-catalyst compounds can be generically representedby the formula:

wherein in each of formulas I and II above:

each A independently represents an at least one of oxygen, sulfur,phosphorous or nitrogen, and preferably represents oxygen or nitrogen ora combination thereof, and most preferably each A in I and at least twoA's of II represent nitrogen;

“a” is an integer of 0, 1 or 2 which represents the number of (L′)groups bound to Z, the value of “a” being dependent on the oxidationstate of Z and whether a particular A—Z bond is dative or covalent, andif covalent whether it is a single or double bond;

Z represents at least one of Group 3 to 10 transition metals of thePeriodic Table, preferably transition metals selected from Fe, Co, Ni,Ru, Rh, Pd, Os, Ir, Pt in the +2(a=0) or +3 (a=1) oxidation state or Ti,V, Cr, Mn, Zr, Hf in the +2 (a=0), +3 (a=1) or +4 (a=2) oxidationstates, more preferably a Group 4 to 7 late transition metal selectedfrom iron, cobalt, nickel or palladium and most preferably iron orcobalt; and each L and L′ (when present) independently represents aligand selected from the group of hydrogen, halo, and hydrocarbon basedradical or group associated through a covalent or dative bond to Z, orboth L groups together represent a hydrocarbon based radical, preferablya C₃ to C₂₄ hydrocarbylene group, associated through a covalent ordative bond to Z, and which, together with Z, constitute a ring or fusedring structure, typically a 3 to 7, preferably 4 to 7 memberheterocyclic ring structure when the line joining A to Z represents acovalent bond.

As used herein, the term “hydrocarbon-based radical or group” denotes aradical or group having a carbon atom directly attached to the remainderof the molecule and having a predominantly hydrocarbon character withinthe context of this invention. Moreover, in this context the terms“group” and “radical” are used interchangeably. Such radicals includethe following:

(1) Hydrocarbon radicals; that is, aliphatic radicals, aromatic- andalicyclic-substituted radicals, and the like, of the type known to thoseskilled in art.

(2) Substituted hydrocarbon radicals; that is, radicals containingpendant non-hydrocarbon substituents, that in the context of thisinvention, do not alter the predominantly hydrocarbon character of theradical or constitute a poison for the pre-catalyst. Those skilled inthe art will be aware of suitable substituents; examples are halo,nitro, hydroxy, alkoxy, carbalkoxy, and alkythio.

(3) Hetero radicals; that is, radicals which, while predominantlyhydrocarbon in character within the context of this invention, containatoms other than carbon present as a member of the linear structure of achain or ring otherwise composed of carbon atoms. Suitable hetero atomswill be apparent to those skilled in the art and include, for example,nitrogen, oxygen and sulfur.

In general, no more than three substituents or hetero atoms, andpreferably no more than one, will be present for each 10 carbon atoms inthe hydrocarbon based radical.

More specifically, the hydrocarbon based radical or group of L and L′can be substituted or unsubstituted, cyclic or non-cyclic, linear orbranched, aliphatic, aromatic, or mixed aliphatic and aromatic includinghydrocarbylene, hydrocarbyloxy, hydrocarbylsilyl, hydrocarbylamino, andhydrocarbylsiloxy radicals having up to 50 non-hydrogen atoms. Thepreferred L and L′ groups are independently selected from halo,hydrocarbyl, and substituted hydrocarbyl radicals. The hydrocarbon basedradical may typically contain from 1 to about 24 carbon atoms,preferably from 1 to about 12 carbon atoms and the substituent group ispreferably a halogen atom.

The lines joining each A to each other A represent a hydrocarbon basedradical, (typically a C₂ to C₉₀ (e.g., C₂ to C₂₀) preferably C₃ to C₃₀(e.g., C₃ to C₁₂) hydrocarbon based radical, such as a hydrocarbyleneradical providing a ring or fused ring hydrocarbylene structure orsubstituted hydrocarbylene structure. Portions of the structure may becomprised of carbon-carbon double bonds, carbon-carbon single bonds,carbon-A atom double bonds and carbon-A atom single bonds.

Typically, for the bidentate and tridentate transition metal compounds,A, Z and the carbons includable in the lines connecting the (A) groupscollectively can be joined to typically make a 4 to 7, preferably 5 to 7member ring structures.

The bonds between each A atom of the pre-catalyst and the transitionmetal Z and between L and Z can be either dative or covalent. Dativebonds merely represent a relationship between an electron rich A atomand the metal Z whereby the electron density of the metal is increasedby providing electrons to the empty orbitals of the metal and do notinduce any change in the oxidation state of the metal Z. Similarconsiderations apply to the relationship between Z and L.

The above described bidentate and tridentate pre-catalyst compounds fromwhich the subject catalyst is derived are known. The disclosure of suchcomponents and the methods of forming the same have been described invarious publications, including PCT Pub. Nos. WO 96/23010; WO 99/46302;WO 99/46303; and WO 99/46304; U.S. Pat. Nos. 5,880,241; 5,880,323;5,866,663; 5,886,224; and 5,891,963; Journal of the American ChemicalSociety (JACS) 1998, 120, 6037-6046, JACS 1995, 117, 6414-6415 andSupplemental Teachings; JACS 1996, 118, 1518; Macromol. Rapid Commun.19, 31-34 (1998); Caltech Highlights 1997, 65-66; Chem Week Apr. 29,1998, 72; C&EN Apr. 13, 1998 11-12; JACS 1998, 120, 4049-4050; JapanesePatent Application 02-078,663, and Angew. Chem. Int. Ed. 1999, vol 38,pp 428-447, The Search for New-Generation Olefin PolymerizationCatalysts: Life Beyond Metallocenes. The teaching of each of the abovecited references are incorporated herein in its entirety by reference.

In formulas I and II, each L and L′ group is preferably a halogen atom,an unsubstituted hydrocarbyl or a hydrocarbyloxy group. The mostpreferred compounds are those having each L being halogen.

Preferred bidentate pre-catalyst compounds may, for example berepresented as compounds of the formula:

wherein

n is an integer which can vary from 0 to 3, preferably 0 or 1;

a, b, c, and d each independently represents a 1 or 0 to indicatewhether its associated R group is present (1) or not (0);

R¹ and R⁴ are each independently selected from an unsubstituted orsubstituted C₁-C₂₀, preferably C₃-C₂₀ hydrocarbyl, such as alkyl, aryl,alkaryl or aralkyl group, as for example, i-propyl; t-butyl;2,4,6-trimethylphenyl; 2-methylphenyl; 2,6-diisopropylphenyl; theirfluorinated derivatives and the like; or with adjacent groups, together,may represent a C₃-C₂₀ hydrocarbylene group;

R², R³, R⁵, R⁶, R⁷, and R⁸ are each independently selected fromhydrogen, an unsubstituted or substituted C₁-C₂₀ hydrocarbyl group suchas an alkyl, aryl, alkaryl or aralkyl group, as for example, methyl,ethyl, i-propyl, butyl (all isomers), phenyl, toluyl,2,6-diisopropylphenyl and the like; or any R groups and adjacent carbonatoms, such as R² and R³, taken together can provide an unsubstituted orsubstituted C₃-C₂₀ ring forming hydrocarbylene group, such as hexylene,1,8-naphthylene and the like.

Z, A and each L and L′ are as defined above in connection with FormulaI. It is preferred that Z be selected from nickel or palladium and thateach L and L′ be independently selected from chlorine, bromine, iodineor a C₁-C₈ (more preferably C₁-C₄) alkyl. The bonds depicted by a dottedline signify the possibility that the atoms bridged by said dotted linemay be bridged by a single or double bond.

It will be understood that the particular identity of b, c, and d inFormula I will be dependent on (i) the identity of Z, (ii) the identityof heteroatom A, (iii) whether the bond between heteroatom A and itsadjacent ring carbon is single or double, and (iv) whether the bondbetween heteroatom A and Z is dative or covalent.

More specifically, when A¹ in Formula Ia is nitrogen it will always haveat least 3 available vacancies for bonding. If the bond between such Nand its adjacent ring carbon is a double covalent bond, the b for R⁵will be zero, and only one further vacancy will be available in the Nfor either a covalent bond with Z, in which case c and d are zero, or ifthe bond with Z is dative, the N can covalently bond with its associatedR¹ or R⁷ group in which case either d or c is 1. Similarly, if the bondsbetween the N and the adjacent ring carbon and between N and Z aresingle covalent, the b of R⁵ can be 1, and either d or the c of R⁷ willbe 1. Alternatively if the bond between N and Z is dative in thisscenario, both d, and the c of R⁷ can be 1.

The above rules are modified when A¹ in Formula Ia is oxygen becauseoxygen has only 2 available vacancies rather than the 3 vacancies for N.Thus, when A¹ is oxygen and is double covalently bonded to the adjacentring carbon, the bond between A¹ and Z will be dative and b of R⁵, c ofR⁷ and d will be 0. If such double bond is replaced by a single bond,the b of R⁵ can be 1 and either the bond between A¹ and Z is singlecovalent, in which case c of R² and d are both 0, or if dative, either cof R⁷ or d can be 1.

The vacancy rules when A¹ is sulfur are the same as for A¹ being oxygen.Phosphorous typically has 3 available vacancies for 3 single covalentbonds or 1 double covalent bond and 1 single covalent bond. Phosphorouswill typically not covalently bond with Z, its association with Z beingthat of a dative bond.

Similar considerations to those described above for A¹ apply in respectto A² of Formula Ia and in respect to all A groups and a, b, c, ofFormula IIa discussed hereinafter.

Illustrative of bidentate pre-catalyst compounds which are useful inproviding the catalyst composition of the present invention arecompounds of Ia having the following combination of groups:

TABLE I Ia

# n R¹/R⁴ R²/R³ R⁵/R⁶ A¹ A² L¹ L² a b c d Z  1 0 2,6-iPr₂Ph Me N/A N NMe e 0 0 0 1 Pd  2 0 2,6-iPr₂Ph Me N/A N N Me Me 0 0 0 1 Pd  3 02,6-iPr₂Ph Me N/A N N Me Br 0 0 0 1 Pd  4 0 2,6-iPr₂Ph Me N/A N N Me Cl0 0 0 1 Pd  5 0 2,6-iPr₂Ph Me N/A N N Br Br 0 0 0 1 Pd  6 0 2,6-iPr₂PhMe N/A N N Cl Cl 0 0 0 1 Pd  7 0 2,6-iPr₂Ph Me N/A N N Br Br 0 0 0 1 Ni 8 0 2,6-iPr₂Ph Me N/A N N Cl Cl 0 0 0 1 Ni  9 0 2,6-iPr₂Ph Me N/A N NMe Me 0 0 0 1 Ni  10 0 2,6-iPr₂Ph Me N/A N N Me Br 0 0 0 1 Ni  11 02,6-iPr₂Ph Me N/A N N Me Cl 0 0 0 1 Ni  12 0 2,6-Me₂Ph Me N/A N N Me e 00 0 1 Pd  13 0 2,6-Me₂Ph Me N/A N N Me Me 0 0 0 1 Pd  14 0 2,6-Me₂Ph MeN/A N N Me Br 0 0 0 1 Pd  15 0 2,6-Me₂Ph Me N/A N N Me Cl 0 0 0 1 Pd  160 2,6-Me₂Ph Me N/A N N Br Br 0 0 0 1 Pd  17 0 2,6-Me₂Ph Me N/A N N Cl Cl0 0 0 1 Pd  18 0 2,6-iPr₂Ph H N/A N N Me e 0 0 0 1 Pd  19 0 2,6-iPr₂Ph HN/A N N Me Me 0 0 0 1 Pd  20 0 2,6-iPr₂Ph H N/A N N Me Br 0 0 0 1 Pd  210 2,6-iPr₂Ph H N/A N N Me Cl 0 0 0 1 Pd  22 0 2,6-iPr₂Ph H N/A N N Br Br0 0 0 1 Pd  23 0 2,6-iPr₂Ph H N/A N N Cl Cl 0 0 0 1 Pd  24 0 2,6-iPr₂PhH N/A N N Br Br 0 0 0 1 Ni  25 0 2,6-iPr₂Ph H N/A N N Cl Cl 0 0 0 1 Ni 26 0 2,6-iPr₂Ph H N/A N N Me Me 0 0 0 1 Ni  27 0 2,6-iPr₂Ph H N/A N NMe Br 0 0 0 1 Ni  28 0 2,6-iPr₂Ph H N/A N N Me Cl 0 0 0 1 Ni  29 02,6-iPr₂Ph An N/A N N Me e 0 0 0 1 Pd  30 0 2,6-iPr₂Ph An N/A N N Me Me0 0 0 1 Pd  31 0 2,6-iPr₂Ph An N/A N N Me Br 0 0 0 1 Pd  32 0 2,6-iPr₂PhAn N/A N N Me Cl 0 0 0 1 Pd  33 0 2,6-iPr₂Ph An N/A N N Br Br 0 0 0 1 Pd 34 0 2,6-iPr₂Ph An N/A N N Cl Cl 0 0 0 1 Pd  35 0 2,6-iPr₂Ph An N/A N NBr Br 0 0 0 1 Ni  36 0 2,6-iPr₂Ph An N/A N N Cl Cl 0 0 0 1 Ni  37 02,6-iPr₂Ph An N/A N N Me Me 0 0 0 1 Ni  38 0 2,6-iPr₂Ph An N/A N N Me Br0 0 0 1 Ni  39 0 2,6-iPr₂Ph An N/A N N Me Cl 0 0 0 1 Ni  40 0 2,6-Me₂PhAn N/A N N Me e 0 0 0 1 Pd  41 0 2,6-Me₂Ph An N/A N N Me Me 0 0 0 1 Pd 42 0 2,6-Me₂Ph An N/A N N Me Br 0 0 0 1 Pd  43 0 2,6-Me₂Ph An N/A N NMe Cl 0 0 0 1 Pd  44 0 2,6-Me₂Ph An N/A N N Br Br 0 0 0 1 Pd  45 02,6-Me₂Ph An N/A N N Cl Cl 0 0 0 1 Pd  46 0 2,6-Me₂Ph H N/A N N Me e 0 00 1 Pd  47 0 2,6-Me₂Ph H N/A N N Me Me 0 0 0 1 Pd  48 0 2,6-Me₂Ph H N/AN N Me Br 0 0 0 1 Pd  49 0 2,6-Me₂Ph H N/A N N Me Cl 0 0 0 1 Pd  50 02,6-Me₂Ph H N/A N N Br Br 0 0 0 1 Pd  51 0 2,6-Me₂Ph H N/A N N Cl Cl 0 00 1 Pd  52 0 2,6-Me₂Ph Me N/A N N Br Br 0 0 0 1 Ni  53 0 2,6-Me₂Ph MeN/A N N Cl Cl 0 0 0 1 Ni  54 0 2,6-Me₂Ph Me N/A N N Me Me 0 0 0 1 Ni  550 2,6-Me₂Ph Me N/A N N Me Br 0 0 0 1 Ni  56 0 2,6-Me₂Ph Me N/A N N Me Cl0 0 0 1 Ni  57 0 2,4,6-Me₃Ph Me N/A N N Me e 0 0 0 1 Pd  58 02,4,6-Me₃Ph Me N/A N N Me Me 0 0 0 1 Pd  59 0 2,4,6-Me₃Ph Me N/A N N MeBr 0 0 0 1 Pd  60 0 2,4,6-Me₃Ph Me N/A N N Me Cl 0 0 0 1 Pd  61 02,4,6-Me₃Ph Me N/A N N Br Br 0 0 0 1 Pd  62 0 2,4,6-Me₃Ph Me N/A N N ClCl 0 0 0 1 Pd  63 0 2,4,6-Me₃Ph Me N/A N N Br Br 0 0 0 1 Ni  64 02,4,6-Me₃Ph Me N/A N N Cl Cl 0 0 0 1 Ni  65 0 2,4,6-Me₃Ph Me N/A N N MeMe 0 0 0 1 Ni  66 0 2,4,6-Me₃Ph Me N/A N N Me Br 0 0 0 1 Ni  67 02,4,6-Me₃Ph Me N/A N N Me Cl 0 0 0 1 Ni  68 0 2,4,6-Me₃Ph H N/A N N Me e0 0 0 1 Pd  69 0 2,4,6-Me₃Ph H N/A N N Me Me 0 0 0 1 Pd  70 02,4,6-Me₃Ph H N/A N N Me Br 0 0 0 1 Pd  71 0 2,4,6-Me₃Ph H N/A N N Me Cl0 0 0 1 Pd  72 0 2,4,6-Me₃Ph H N/A N N Br Br 0 0 0 1 Pd  73 02,4,6-Me₃Ph H N/A N N Cl Cl 0 0 0 1 Pd  74 0 2,4,6-Me₃Ph H N/A N N Br Br0 0 0 1 Ni  75 0 2,4,6-Me₃Ph H N/A N N Cl Cl 0 0 0 1 Ni  76 02,4,6-Me₃Ph H N/A N N Me Me 0 0 0 1 Ni  77 0 2,4,6-Me₃Ph H N/A N N Me Br0 0 0 1 Ni  78 0 2,4,6-Me₃Ph H N/A N N Me Cl 0 0 0 1 Ni  79 02,4,6-Me₃Ph An N/A N N Me e 0 0 0 1 Pd  80 0 2,4,6-Me₃Ph An N/A N N MeMe 0 0 0 1 Pd  81 0 2,4,6-Me₃Ph An N/A N N Me Br 0 0 0 1 Pd  82 02,4,6-Me₃Ph An N/A N N Me Cl 0 0 0 1 Pd  83 0 2,4,6-Me₃Ph An N/A N N BrBr 0 0 0 1 Pd  84 0 2,4,6-Me₃Ph An N/A N N Cl Cl 0 0 0 1 Pd  85 02,4,6-Me₃Ph An N/A N N Br Br 0 0 0 1 Ni  86 0 2,4,6-Me₃Ph An N/A N N ClCl 0 0 0 1 Ni  87 0 2,4,6-Me₃Ph An N/A N N Me Me 0 0 0 1 Ni  88 02,4,6-Me₃Ph An N/A N N Me Br 0 0 0 1 Ni  89 0 2,4,6-Me₃Ph An N/A N N MeCl 0 0 0 1 Ni  90 0 Ph j N/A N N Me Me 0 0 0 1 Pd  91 0 Ph Me N/A N N MeMe 0 0 0 1 Pd  92 0 Ph H N/A N N Me Me 0 0 0 1 Pd  93 0 Ph An N/A N N MeMe 0 0 0 1 Pd  94 0 Ph j N/A N N Me Cl 0 0 0 1 Pd  95 0 Ph Me N/A N N MeCl 0 0 0 1 Pd  96 0 Ph H N/A N N Me Cl 0 0 0 1 Pd  97 0 Ph An N/A N N MeCl 0 0 0 1 Pd  98 0 2-PhPh j N/A N N Me Me 0 0 0 1 Pd  99 0 2-PhPh MeN/A N N Me Me 0 0 0 1 Pd 100 0 2-PhPh H N/A N N Me Me 0 0 0 1 Pd 101 02-PhPh An N/A N N Me Me 0 0 0 1 Pd 102 0 2-PhPh j N/A N N Me Cl 0 0 0 1Pd 103 0 2-PhPh Me N/A N N Me Cl 0 0 0 1 Pd 104 0 2-PhPh H N/A N N Me Cl0 0 0 1 Pd 105 0 2-PhPh An N/A N N Me Cl 0 0 0 1 Pd 106 0 2,6-EtPh j N/AN N Me Me 0 0 0 1 Pd 107 0 2,6-EtPh Me N/A N N Me Me 0 0 0 1 Pd 108 02,6-EtPh H N/A N N Me Me 0 0 0 1 Pd 109 0 2,6-EtPh An N/A N N Me Me 0 00 1 Pd 110 0 2,6-EtPh j N/A N N Me Cl 0 0 0 1 Pd 111 0 2,6-EtPh Me N/A NN Me Cl 0 0 0 1 Pd 112 0 2,6-EtPh H N/A N N Me Cl 0 0 0 1 Pd 113 02,6-EtPh An N/A N N Me Cl 0 0 0 1 Pd 114 0 2-t-BuPh j N/A N N Me Me 0 00 1 Pd 115 0 2-t-BuPh Me N/A N N Me Me 0 0 0 1 Pd 116 0 2-t-BuPh H N/A NN Me Me 0 0 0 1 Pd 117 0 2-t-BuPh An N/A N N Me Me 0 0 0 1 Pd 118 02-t-BuPh j N/A N N Me Cl 0 0 0 1 Pd 119 0 2-t-BuPh Me N/A N N Me Cl 0 00 1 Pd 120 0 2-t-BuPh H N/A N N Me Cl 0 0 0 1 Pd 121 0 2-t-BuPh An N/A NN Me Cl 0 0 0 1 Pd 122 0 1-Np j N/A N N Me Me 0 0 0 1 Pd 123 0 1-Np MeN/A N N Me Me 0 0 0 1 Pd 124 0 1-Np H N/A N N Me Me 0 0 0 1 Pd 125 01-Np An N/A N N Me Me 0 0 0 1 Pd 126 0 PhMe j N/A N N Me Cl 0 0 0 1 Pd127 0 PhMe Me N/A N N Me Cl 0 0 0 1 Pd 128 0 PhMe H N/A N N Me Cl 0 0 01 Pd 129 0 PhMe An N/A N N Me Cl 0 0 0 1 Pd 130 0 PhMe j N/A N N Me Me 00 0 1 Pd 131 0 PhMe Me N/A N N Me Me 0 0 0 1 Pd 132 0 PhMe H N/A N N MeMe 0 0 0 1 Pd 133 0 PhMe An N/A N N Me Me 0 0 0 1 Pd 134 0 PhMe j N/A NN Me Cl 0 0 0 1 Pd 135 0 PhMe Me N/A N N Me Cl 0 0 0 1 Pd 136 0 PhMe HN/A N N Me Cl 0 0 0 1 Pd 137 0 PhMe An N/A N N Me Cl 0 0 0 1 Pd 138 0Ph₂Me j N/A N N Me Me 0 0 0 1 Pd 139 0 Ph₂Me Me N/A N N Me Me 0 0 0 1 Pd140 0 Ph₂Me H N/A N N Me Me 0 0 0 1 Pd 141 0 Ph₂Me An N/A N N Me Me 0 00 1 Pd 142 0 Ph₂Me j N/A N N Me Cl 0 0 0 1 Pd 143 0 Ph₂Me Me N/A N N MeCl 0 0 0 1 Pd 144 0 Ph₂Me H N/A N N Me Cl 0 0 0 1 Pd 145 0 Ph₂Me An N/AN N Me Cl 0 0 0 1 Pd 146 0 2,6-t-BuPh j N/A N N Me Me 0 0 0 1 Pd 147 02,6-t-BuPh Me N/A N N Me Me 0 0 0 1 Pd 148 0 2,6-t-BuPh H N/A N N Me Me0 0 0 1 Pd 149 0 2,6-t-BuPh An N/A N N Me Me 0 0 0 1 Pd 150 0 2,6-t-BuPhj N/A N N Me Cl 0 0 0 1 Pd 151 0 2,6-t-BuPh Me N/A N N Me Cl 0 0 0 1 Pd152 0 2,6-t-BuPh H N/A N N Me Cl 0 0 0 1 Pd 153 0 2,6-t-BuPh An N/A N NMe Cl 0 0 0 1 Pd 154 0 2,6-t-BuPh H N/A N N Br Br 0 0 0 1 Ni 155 02,6-t-Bu₂Ph Me N/A N N Br Br 0 0 0 1 Ni 156 0 2,6-t-Bu₂Ph An N/A N N BrBr 0 0 0 1 Ni 157 0 2,6-t-Bu₂Ph H N/A N N Br Br 0 0 0 1 Ni 158 02,6-t-Bu₂Ph Me N/A N N Br Br 0 0 0 1 Ni 159 0 2-6-t-Bu₂Ph An N/A N N BrBr 0 0 0 1 Ni 160 0 Ph H N/A N N Br Br 0 0 0 1 Ni 161 0 Ph Me N/A N N BrBr 0 0 0 1 Ni 162 0 Ph An N/A N N Br Br 0 0 0 1 Ni 163 0 2-PhPh H N/A NN Br Br 0 0 0 1 Ni 164 0 2-PhPh Me N/A N N Br Br 0 0 0 1 Ni 165 0 2-PhPhAn N/A N N Br Br 0 0 0 1 Ni 166 0 2-iPr-6-MePh H N/A N N Br Br 0 0 0 1Ni 167 0 2-iPr-6-MePh Me N/A N N Br Br 0 0 0 1 Ni 168 0 2-iPr-6-MePh AnN/A N N Br Br 0 0 0 1 Ni 169 0 2,5-t-BuPh H N/A N N Br Br 0 0 0 1 Ni 1700 2,5-t-BuPh Me N/A N N Br Br 0 0 0 1 Ni 171 0 2,5-t-BuPh An N/A N N BrBr 0 0 0 1 Ni 172 0 2,6-EtPh H N/A N N Br Br 0 0 0 1 Ni 173 0 2,6-EtPhMe N/A N N Br Br 0 0 0 1 Ni 174 0 2,6-EtPh An N/A N N Br Br 0 0 0 1 Ni175 0 1-Np H N/A N N Br Br 0 0 0 1 Ni 176 0 1-Np Me N/A N N Br Br 0 0 01 Ni 177 0 1-Np An N/A N N Br Br 0 0 0 1 Ni 178 0 Ph Ph N/A N N Br Br 00 0 1 Ni 179 0 2,4,6-Me₃Ph H N/A N N Br Br 0 0 0 1 Ni 180 0 2,4,6-Me₃PhMe N/A N N Br Br 0 0 0 1 Ni 181 0 2,4,6-Me₃Ph An N/A N N Br Br 0 0 0 1Ni 182 0 2,4,6-Me₃Ph Ph N/A N N Br Br 0 0 0 1 Ni 183 1 2,6-Pr₂Pr H H N NCl Cl 0 0 0 1 SY 184 2 2,6-Pr₂Pr H H N N Cl Cl 0 0 0 1 SY 185 32,6-Pr₂Pr H H N N Cl Cl 0 0 0 1 SY 186 1 2,6-Pr₂Pr Me Me N N Cl Cl 0 0 01 SY 187 2 2,6-Pr₂Pr Me Me N N Cl Cl 0 0 0 1 SY 188 3 2,6-Pr₂Pr Me Me NN Cl Cl 0 0 0 1 SY 189 1 2,6-Me₂Ph H H N N Cl Cl 0 0 0 1 SY 190 22,6-Me₂Ph H H N N Cl Cl 0 0 0 1 SY 191 3 2,6-Me₂Ph H H N N Cl Cl 0 0 0 1SY 192 1 2,6-Me₂Ph Me Me N N Cl Cl 0 0 0 1 SY 193 2 2,6-Me₂Ph Me Me N NCl Cl 0 0 0 1 SY 194 3 2,6-Me₂Ph Me Me N N Cl Cl 0 0 0 1 SY 195 12,4,6-Me₃Ph H H N N Cl Cl 0 0 0 1 SY 196 2 2,4,6-Me₃Ph H H N N Cl Cl 0 00 1 SY 197 3 2,4,6-Me₃Ph H H N N Cl Cl 0 0 0 1 SY 198 1 2,4,6-Me₃Ph MeMe N N Cl Cl 0 0 0 1 SY 199 2 2,4,6-Me₃Ph Me Me N N Cl Cl 0 0 0 1 SY 2003 2,4,6-Me₃Ph Me Me N N Cl Cl 0 0 0 1 SY *201  1 2,6-iPr₂Ph H H N N ClCl 1 0 0 1 CMW 202 2 2,6-iPr₂Ph H H N N Cl Cl 1 0 0 1 CMW 203 32,6-iPr₂Ph H H N N Cl Cl 1 0 0 1 CMW 204 1 2,6-iPrPh Me Me N N Cl Cl 1 00 1 CMW 205 2 2,6-iPrPh Me Me N N Cl Cl 1 0 0 1 CMW 206 3 2,6-iPrPh MeMe N N Cl Cl 1 0 0 1 CMW 207 1 2,6-Me₂Ph H H N N Cl Cl 1 0 0 1 CMW 208 22,6,Me₂Ph H H N N Cl Cl 1 0 0 1 CMW 209 3 2,6,Me₂Ph H H N N Cl Cl 1 0 01 CMW 210 1 2,6,Me₂Ph Me Me N N Cl Cl 1 0 0 1 CMW 211 2 2,6,Me₂Ph Me MeN N Cl Cl 1 0 0 1 CMW 212 3 2,6,Me₂Ph Me Me N N Cl Cl 1 0 0 1 CMW 213 12,4,6-Me₃Ph H H N N Cl Cl 1 0 0 1 CMW 214 2 2,4,6-Me₃Ph H H N N Cl Cl 10 0 1 CMW 215 3 2,4,6-Me₃Ph H H N N Cl Cl 1 0 0 1 CMW 216 1 2,4,6-Me₃PhMe Me N N Cl Cl 1 0 0 1 CMW 217 2 2,4,6-Me₃Ph Me Me N N Cl Cl 1 0 0 1CMW 218 3 2,4,6-Me₃Ph Me Me N N Cl Cl 1 0 0 1 CMW 219 1 2,6 iPr₂Ph H H NN Cl Cl 1 0 0 1 TZH 220 2 2,6 iPr₂Ph H H N N Cl Cl 1 0 0 1 TZH 221 3 2,6iPr₂Ph H H N N Cl Cl 1 0 0 1 TZH 222 1 2,6 iPr₂Ph Me Me N N Cl Cl 1 0 01 TZH 223 2 2,6 iPr₂Ph Me Me N N Cl Cl 1 0 0 1 TZH 224 3 2,6 iPr₂Ph MeMe N N Cl Cl 1 0 0 1 TZH 225 1 2,6-Me₂Ph H H N N Cl Cl 1 0 0 1 TZH 226 22,6-Me₂Ph H H N N Cl Cl 1 0 0 1 TZH 227 3 2,6-Me₂Ph H H N N Cl Cl 1 0 01 TZH 228 1 2,6-Me₂Ph Me Me N N Ci Cl 1 0 0 1 TZH 229 2 2,6-Me₂Ph Me MeN N Cl Cl 1 0 0 1 TZH 230 3 2,6-Me₂Ph Me Me N N Cl Cl 1 0 0 1 TZH 231 12,4,6-Me₃Ph H H N N Cl Cl 1 0 0 1 TZH 232 2 2,4,6-Me₃Ph H H N N Cl Cl 10 0 1 TZH 233 3 2,4,6-Me₃Ph H H N N Cl Cl 1 0 0 1 TZH 234 1 2,4,6-Me₃PhMe Me N N Cl Cl 1 0 0 1 TZH 235 2 2,4,6-Me₃Ph Me Me N N Cl Cl 1 0 0 1TZH 236 3 2,4,6-Me₃Ph Me Me N N Cl Cl 1 0 0 1 TZH e = the group(CH₂)₃CO₂Me *L′ is Cl for #'s 201 to 236

Note—In Table I, above, the following convention and abbreviations areused. For R¹ and R⁴, when a substituted phenyl ring is present, theamount of substitution is indicated by the number of numbers indicatingpositions on the phenyl ring, as, for example, 2,6-iPr₂Ph represents2,6-diisopropyl phenyl; iPr=isopropyl; Pr=propyl; Me=methyl; Et=ethyl;t-Bu=tert-butyl; Ph=phenyl; Np=naphthyl; An=1,8-naphthalene; j is thegroup —C(Me)₂—CH₂—C(Me)₂—; and e is the group (CH₂)₃CO₂Me-, SY=Sc or Y;CMW=Cr, Mo or W; TZH=Ti, Zr, or Hf and N/A=not applicable.

The typical tridentate pre-catalyst compounds may, for example, berepresented by the formula:

wherein:

R⁵ and R⁶ are each independently selected from hydrogen, or anunsubstituted or substituted aryl group wherein said substitution is analkyl or a functional hetero group which is inert with respect to thecontemplated polymerization;

R⁷ and R⁸ are each independently selected from hydrogen, anunsubstituted or substituted C₁-C₂₀ (preferably C₁-C₆) hydrocarbyl as,for example, alkyl (methyl, ethyl, propyl, pentyl and the like); aryl(phenyl, toluyl and the like) or a functional group which is inert withrespect to the polymerization (e.g., nitro, halo and the like);

R⁹ to R¹⁹ are each independently selected from hydrogen, anunsubstituted or substituted C₁-C₂₀ hydrocarbyl or an inert functionalgroup, all as described above for R⁷;

a, b and c are each independently 0 or 1 and represent whether theirassociated R group is present or not;

Z is a transition metal as defined above, preferably Fe(II), Co(II) orFe(III);

each A¹ to A³ is independently selected as defined in connection with Aof Formula I;

and each L and L′ is independently selected from a halogen such aschlorine, bromine, iodine or a C₁-C₈ (preferably C₁-C₅) alkyl, or anytwo L groups, together in combination, represent an unsubstituted orsubstituted, saturated or unsaturated, hydrocarbylene group whichtogether with Z forms a cyclic group, preferably a 3 to 7, mostpreferably 3 to 5 member ring cyclic group.

Preferred compounds of II(a) are those wherein each R⁹, R¹⁰ and R¹¹ arehydrogen; b is 0, c is 1, and R⁷ and R⁸ are each independently selectedfrom halogen, hydrogen or a C₁-C₆ alkyl, preferably each isindependently selected from methyl or hydrogen; and wherein R⁵ and R⁶ ofIIa are each an aryl or substituted aryl group, preferably wherein thearyl contains substitution in the 2 position, the 2,6 positions or the2,4,6 positions which is selected from a C₁-C₆ (most preferably C₁-C₃)alkyl and the remaining positions are each independently selected fromhydrogen (most preferred), halogen or a C₁-C₆ (preferably C₁-C₃) alkyl.

Illustrative examples of tridentate pre-catalyst compounds which areuseful in providing the catalyst composition of the present inventionare compounds of Formula IIa having the following combination of groupsshown in Table II below:

TABLE II IIa

# R⁵/R⁶ R⁷/R⁸ R⁹ R¹⁰ R¹¹ A¹ A² A³ a b c L L′ Z  1 2,6-di-iPrPh Me H H HN N N 0 0 1 * NA Fe  2 2,6-di-iPrPh Me H H H N N N 0 0 1 * NA Fe  32-t-BuPh Me H H H N N N 0 0 1 * NA Fe  4 Ph Me H H H N N N 0 0 1 * NA Fe 5 2,6-di-iPrPh Me H Me H N N N 0 0 1 * NA Fe  6 2,6-di-iPrPh Me H Me HN N N 0 0 1 * NA Fe  7 2-t-BuPh Me H Me H N N N 0 0 1 * NA Fe  8 Ph Me HMe H N N N 0 0 1 * NA Fe  9 2,6-di-iPrPh Me Me Me Me N N N 0 0 1 * NA Fe10 2,6-di-iPrPh Me Me Me Me N N N 0 0 1 * NA Fe 11 2-t-BuPh Me Me Me MeN N N 0 0 1 * NA Fe 12 Ph Me Me Me Me N N N 0 0 1 * NA Fe 13 2,4,6-Me₃PhMe H H H N N N 0 0 1 * NA Fe 14 2,3,4,5,6-Me₅Ph Me H H H N N N 0 0 1 *NA Fe 15 (2-t-BuMe₂Sil)Bz Me H H H N N N 0 0 1 * NA Fe 16 (2-Me₃Sil)BzMe H H H N N N 0 0 1 * NA Fe 17 (2-PhMe₂Sil)Bz Me H H H N N N 0 0 1 * NAFe 18 (2-PhMeSil)Bz Me H H H N N N 0 0 1 * NA Fe 19 (2-Me₂Sil)Bz Me H HH N N N 0 0 1 * NA Fe 20 2,6-di-iPrPh Me H H H N N N 0 0 1 * NA Co 212,6-di-iPrPh Me H H H N N N 0 0 1 * NA Co 22 2-t-BuPh Me H H H N N N 0 01 * NA Co 23 Ph Me H H H N N N 0 0 1 * NA Co 24 2,6-di-iPrPh Me H Me H NN N 0 0 1 * NA Co 25 2,6-di-iPrPh Me H Me H N N N 0 0 1 * NA Co 262-t-BuPh Me H Me H N N N 0 0 1 * NA Co 27 Ph Me H Me H N N N 0 0 1 * NACo 28 2,6-di-iPrPh Me Me Me Me N N N 0 0 1 * NA Co 29 2,6-di-iPrPh Me MeMe Me N N N 0 0 1 * NA Co 30 2-t-BuPh Me Me Me Me N N N 0 0 1 * NA Co 31Ph Me Me Me Me N N N 0 0 1 * NA Co 32 2,4,6-(Me)₃Ph Me H H H N N N 0 01 * NA Co 33 2,3,4,5,6-(Me)₅Ph Me H H H N N N 0 0 1 * NA Co 34(2-t-BuMe₂Sil)Bz Me H H H N N N 0 0 1 * NA Co 35 2-MePh Me H H H N N N 00 1 * NA Fe 36 (2-Me₃Sil)Bz Me H H H N N N 0 0 1 * NA Co 37(2-PhMe₂Sil)Bz Me H H H N N N 0 0 1 * NA Co 38 (2-PhMeSil)Bz Me H H H NN N 0 0 1 * NA Co 39 (2-Me₃Sil)Bz Me H H H O N 0 0 0 0 * NA Co 40 NA MeH H H O N 0 0 0 0 * NA Fe 41 NA Me H Me H O N 0 0 0 0 * NA Fe 42 NA i-PrH H H O N 0 0 0 0 * NA Fe 43 NA i-Pr H Me H O N 0 0 0 0 * NA Fe 44 NAi-Pr Me Me Me O N 0 0 0 0 * NA Fe 45 NA Ph H H H O N 0 0 0 0 * NA Fe 46NA Ph H Me H O N 0 0 0 0 * NA Fe 47 NA Me H H H O N 0 0 0 0 * NA Co 48NA Me H Me H O N 0 0 0 0 * NA Co 49 NA i-Pr H H H O N 0 0 0 0 * NA Co 50NA i-Pr H Me H O N 0 0 0 0 * NA Co 51 NA i-Pr Me Me Me O N 0 0 0 0 * NACo 52 NA Ph H H H O N 0 0 0 0 * NA Co 53 NA Ph H Me H O N 0 0 0 0 * NACo 54 2,6-iPr₂Ph Me H F H N N N 1 0 1 Cl Cl VNT 55 2,6-iPr₂Ph Me H Cl HN N N 1 0 1 Cl Cl VNT 56 2,6-iPr₂Ph Me H Br H N N N 1 0 1 Cl Cl VNT 572,6-iPr₂Ph Me H I H N N N 1 0 1 Cl Cl VNT 58 2,6-iPr₂Ph Me H H H N N N 10 1 Cl Cl VNT 59 2,6-iPr₂Ph Me H H H N N N 1 0 1 Cl Cl VNT 60 2,6-iPr₂PhH H F H N N N 1 0 1 Cl Cl VNT 61 2,6-iPr₂Ph H H Cl H N N N 1 0 1 Cl ClVNT 62 2,6-iPr₂Ph H H Br H N N N 1 0 1 Cl Cl VNT 63 2,6-iPr₂Ph H H I H NN N 1 0 1 Cl Cl VNT 64 2,6-Me₂Ph Me H H H N N N 1 0 1 Cl Cl VNT 652,6-Me₂Ph Me H F H N N N 1 0 1 Cl Cl VNT 66 2,6-Me₂Ph Me H Cl H N N N 10 1 Cl Cl VNT 67 2,6-Me₂Ph Me H B H N N N 1 0 1 Cl Cl VNT 68 2,6-Me₂PhMe H I H N N N 1 0 1 Cl Cl VNT 69 2,6-Me₂Ph H H H H N N N 1 0 1 Cl ClVNT 70 2,6-Me₂Ph H H F H N N N 1 0 1 Cl Cl VNT 71 2,6-Me₂Ph H H Cl H N NN 1 0 1 Cl Cl VNT 72 2,6-Me₂Ph H H Br H N N N 1 0 1 Cl Cl VNT 732,6-Me₂Ph H H I H N N N 1 0 1 Cl Cl VNT 74 2,4,6-Me₃Ph Me H H H N N N 10 1 Cl Cl VNT 75 2,4,6-Me₃Ph Me H F H N N N 1 0 1 Cl Cl VNT 762,4,6-Me₃Ph Me H Cl H N N N 1 0 1 Cl Cl VNT 77 2,4,6-Me₃Ph Me H Br H N NN 1 0 1 Cl Cl VNT 78 2,4,6-Me₃Ph H H I H N N N 1 0 1 Cl Cl VNT 792,4,6-Me₃Ph H H H H N N N 1 0 1 Cl Cl VNT 80 2,4,6-Me₃Ph H H F H N N N 10 1 Cl Cl VNT 81 2,4,6-Me₃Ph H H Cl H N N N 1 0 1 Cl Cl VNT 822,4,6-Me₃Ph H H Br H N N N 1 0 1 Cl Cl VNT 83 2,4,6-Me₃Ph H H I H N N N1 0 1 Cl Cl VNT 84 2,6-iPr₂Ph H H H H N N N 1 0 1 Cl Cl MTR 852,6-iPr₂Ph H H F H N N N 1 0 1 Cl Cl MTR 86 2,6-iPr₂Ph H H Cl H N N N 10 1 Cl Cl MTR 87 2,6-iPr₂Ph H H B H N N N 1 0 1 Cl Cl MTR 88 2,6-iPr₂PhH H I H N N N 1 0 1 Cl Cl MTR 89 2,6-iPr₂Ph Me H H H N N N 1 0 1 Cl ClMTR 90 2,6-iPr₂Ph Me H F H N N N 1 0 1 Cl Cl MTR 91 2,6-iPr₂Ph Me H Cl HN N N 1 0 1 Cl Cl MTR 92 2,6-iPr₂Ph Me H Br H N N N 1 0 1 Cl Cl MTR 932,6-iPr₂Ph Me H I H N N N 1 0 1 Cl Cl MTR 94 2,6-Me₂Ph H H H H N N N 1 01 Cl Cl MTR 95 2,6-Me₂Ph H H F H N N N 1 0 1 Cl Cl MTR 96 2,6-Me₂Ph H HCl H N N N 1 0 1 Cl Cl MTR 97 2,6-Me₂Ph H H B H N N N 1 0 1 Cl Cl MTR 982,6-Me₂Ph H H I H N N N 1 0 1 Cl Cl MTR 99 2,6-Me₂Ph Me H H H N N N 1 01 Cl Cl MTR 100  2,6-Me₂Ph Me H F H N N N 1 0 1 Cl Cl MTR 101  2,6-Me₂PhMe H Cl H N N N 1 0 1 Cl Cl MTR 102  2,6-Me₂Ph Me H Br H N N N 1 0 1 ClCl MTR 103  2,6-Me₂Ph Me H I H N N N 1 0 1 Cl Cl MTR 104  2,4,6-Me₃Ph HH H H N N N 1 0 1 Cl Cl MTR 105  2,4,6-Me₃Ph H H F H N N N 1 0 1 Cl ClMTR 106  2,4,6-Me₃Ph H H Cl H N N N 1 0 1 Cl Cl MTR 107  2,4,6-Me₃Ph H HB H N N N 1 0 1 Cl Cl MTR 108  2,4,6-Me₃Ph H H I H N N N 1 0 1 Cl Cl MTR109  2,4,6-Me₃Ph Me H H H N N N 1 0 1 Cl Cl MTR 110  2,4,6-Me₃Ph Me H FH N N N 1 0 1 Cl Cl MTR 111  2,4,6-Me₃Ph Me H Cl H N N N 1 0 1 Cl Cl MTR112  2,4,6-Me₃Ph Me H Br H N N N 1 0 1 Cl Cl MTR 113  2,4,6-Me₃Ph Me H IH N N N 1 0 1 Cl Cl MTR NA = Not Applicable VNT = V, Nb, or Ta MTR = Mn,Tc, or Re

The asterisk (*) in Table II above represents both anionic ligand groups(L) of the above preferred tridentate compounds II(a) and for each ofthe above compounds both L groups are, respectively, chlorine; bromine;methyl (—CH₃); ethyl (—C₂H₅); propyl (—C₃H₅, each of the isomers); butyl(—C₄H₉, each of the isomers); dimethylamine; 1,3-butadiene-1,4 diyl;1,4-pentadiene-1,5 diyl; C₄ alkylene; and C₅ alkylene. Also in Table IIB_(z)=benzyl; Sil=siloxyl; iPrPh=isopropylphenyl; t-Bu=tert-butyl;Me₂=dimethyl, Me₃=trimethyl, etc.

It will be understood that the identity of L will determine the natureof the process steps needed to form the ultimate catalyst compositionwhich is believed to exist, during polymerization, as an activated pairof a cation, or cation like (referred to herein collectively asCationic) component and an anion or anion like (referred to hereincollectively as Anionic) component. The Cationic component is thepre-catalyst which has undergone activation typically by imparting afull or partial positive charge to the metal center Z and the Anioniccomponent is a full or partial negatively charged component derived fromthe support-activator and is believed to be in close proximity to, andprovides charge balance for, the activated metal center Z underconventional polymerization reaction conditions while remaining labile.The term “labile” is used herein to mean that under polymerizationconditions, the anionic component is only loosely associated at the siteof the catalyst activity so as to permit displacement by a polymerizablemonomer at the point of monomer addition.

Thus, the manner in which the pre-catalyst is activated typicallydepends on the identity of L.

From a generic standpoint, activation of pre-catalyst is believed toresult from removal of at least one L group from the metal center in amanner sufficient to generate an open coordination site at said metalcenter.

A variety of mechanisms and materials are known or possible foraccomplishing activation. Depending on the identity of L and thesupport-activator, such mechanisms may be induced in 1 or 2 stages(relative to a designated molecule). Activation in a single stagetypically involves separately synthesizing a pre-catalyst that can beactivated directly by the support-activator (e.g., wherein L isinitially selected as hydrocarbyl in the synthesis of the pre-catalyst).Activation in 2 stages typically involves a pre-activation first stagewherein at least one electronic withdrawing L group (e.g. Cl) isreplaced with at least one less electronic withdrawing L group (e.g.,alkyl) which is more easily displaced in the second stage by thesupport-activator to cause activation at the metal center Z.Accordingly, pre-activation can be induced via known alkylationreactions with organometallic compounds, such as organolithium orpreferably organoaluminum hydrides or alkyls. Pre-activation permits oneto use the support-activator in all instances for activation andeliminate use of expensive methylalumoxane or ionizing agents such asboron containing activators (or co-catalysts).

Thus, while activation mechanisms by which conventional coordinationcatalyst systems operate include, but are not limited to (a) abstractionof at least one L group by a Lewis acid by an abstracting moiety such ascarbonium, tropylium, carbenium, ferrocenium and mixtures, and (b)protonation (by a Bronstead acid) of the L group, when L constitutes ahydride or hydrocarbyl (e.g. alkyl) group, such mechanisms typicallyrequire materials additional to the support for implementation. The sameis not true for the present invention.

It is a particular advantage of the present invention that suchconventional ionizing agents used to produce ionic catalysts can beeliminated and replaced with the support-activator of the presentinvention which performs the dual function of activation and supportingagent.

From a practical standpoint, it is preferred that L be halogen, e.g.,Cl, in the pre-catalyst. This stems from the fact that when L is halogen(highly electron withdrawing) the pre-catalyst is very stable and can beeasily transported. However, because L in this instance is highlyelectron withdrawing, it may be more difficult to induce activationthereof by the support-activator. Thus, as indicated above, it ispossible to pre-activate the pre-catalyst, by replacement of thehalogens constituting L with less electron withdrawing groups such ashydrocarbyl groups, e.g., alkyl groups, using organometallic compounds.The particular point in time when the organometallic compound contactsthe pre-catalyst is at the option of the manufacturer and can be (a)before, during or after contact of the support-activator withpre-catalyst prior to entry into the polymerization zone and/or (b) uponor during polymerization by direct addition to the polymerization zone.However, because pre-activated catalysts are less stable than thehalogenated precursors thereof, organometallic compound addition, whenemployed, is preferably conducted in the presence of thesupport-activator. It is a further particular advantage of the presentinvention that activation of the pre-catalyst (having L=halogen) can bedelayed by avoiding the use of the organometallic compound to inducepre-activation until polymerization occurs. Thus, such pre-catalyst canbe impregnated into the support activator and the same recovered withoutactivation until used for polymerization. Since it is possible to employlower total amounts of organometallic compound by adding it only to thereactor during polymerization, this is the preferred approach.

Thus, one preferred embodiment comprises using pre-catalyst transitionmetal compound I or II wherein each L group is a halogen atom. In thisembodiment the pre-catalyst and support-activator are separately mixed.In another embodiment said pre-catalyst, support-activator and at leastone organometallic compound (represented by Formula III below) areadmixed simultaneously prior to polymerization. In this embodiment, atleast one of the halogens constituting L becomes a new hydrocarbyl Lgroup derived from the organometallic, i.e., compound duringpre-activation. More specifically, when used as a scavenging andalkylating agent, the organometallic compound is typically addeddirectly to the polymerization zone, whereas when employed as analkylating agent alone it is desirably added to the mixture ofsupport-activator and pre-catalyst.

Organometallic compounds suitable for use in pre-activation includethose represented by Formula (III):

M(R¹²)_(s)  III

wherein M represents an element of the Group 1, 2 or 13 of the PeriodicTable, a tin atom or a zinc atom; each R¹² independently represents ahydrogen atom, a halogen atom, a hydrocarbon based radical such ashydrocarbyl, typically C₁ to C₂₄ hydrocarbyl, including C₁ to C₂₄ alkylor alkoxy and aryl, aryloxy, arylalkyl, arylalkoxy, alkylaryl oralkylaryloxy group having 6 to 24 carbon atoms (such as a hydrogen atom,halogen atom (e.g., chlorine fluorine, bromine, iodine and mixturesthereof), alkyl groups (e.g., methyl, ethyl, propyl, pentyl, hexyl,heptyl, decyl, isopropyl, isobutyl, s-butyl, t-butyl), alkoxy groups(e.g., methyoxy, ethoxy, propoxy, butoxy, isopropoxy), aryl groups(e.g., phenyl, biphenyl, naphthyl), aryloxy groups (e.g., phenoxy),arylalkyl groups (e.g., benzyl, phenylethyl), arylalkoxy groups(benzyloxy), alkylaryl groups (e.g., tolyl, xylyl, cumenyl, mesityl),and alkylaryloxy groups (e.g., methylphenoxy) and s is the oxidationnumber of M. Preferably at least one R¹² is hydrocarbyl, e.g., an alkylgroup having 1 to 24 carbon atoms or an aryl, arylalkyl or alkylarylgroup having 6 to 24 carbon atoms, e.g., to provide a source ofhydrocarbyl groups for alkylation of the pre-catalyst when L isnon-hydrocarbyl.

The preferred organometallic compounds are those wherein M is aluminum.

Representative examples of organometallic compounds include alkylaluminum compounds, preferably trialkyl aluminum compounds, such astrimethyl aluminum, triethyl aluminum, triisopropyl aluminum,triisobutyl aluminum, tri-n-propylaluminum, triisobutylaluminum,tri-n-butylaluminum, triamylaluminum, and the like; alkyl aluminumalkoxides such as ethyl aluminum diethoxide, diisobutyl aluminumethoxide, di(tert-butyl) aluminum butoxide, diisopropyl aluminumethoxide, dimethyl aluminum ethoxide, diethyl aluminum ethoxide,di-n-propyl aluminum ethoxide, di-n-butyl aluminum ethoxide, and thelike; aluminum alkoxides such as aluminum ethoxide, aluminum propoxide,aluminum butoxide and the like; alkyl or aryl aluminum halides such asdiethyl aluminum chloride, ethyl aluminum dichloride, diisopropylaluminum chloride and the like; aluminum aryloxides such as aluminumphenoxide, and the like; and mixed aryl, alkyl or aryloxy, alkylaluminum compounds and aluminum hydrides such as dimethylaluminumhydride, diethylaluminum hydride, diisopropylaluminum hydride,di-n-propylaluminum hydride, diisobutylaluminum hydride, anddi-n-butylaluminum hydride. The most preferred organometallic compoundsare the trialkyl aluminum compounds.

When at least one L of the transition metal compounds is halogen, thepre-catalyst and/or the organometallic compound can be mixed in an inertdiluent prior to, simultaneously with, or after contact (of either one)with the support-activator. The pre-catalyst, when two L groups arehalogen, is more stable to materials which are poisons to the activatedcatalyst.

In a second preferred embodiment wherein each L of the pre-catalyst is ahydrocarbyl, a hydrocarbylene or a hydrocarbyloxy group, there is noneed for the addition or handling of the organometallic compound. Thus,the catalyst composition can be readily formed and used withoutpre-activation. However, even in this instance, it is still preferred toemploy at least some organometallic compound as a scavenger duringpolymerization to deactivate potential poisons to the activatedcatalyst.

The support-activator is a composite in the form of agglomerates of atleast two components, namely, (A) at least one inorganic oxide componentand (B) at least one ion-containing layered component.

In addition, the morphology of the support-activator is believed tosignificantly influence the performance of the catalyst composition.

The inorganic oxide Component-A of the support-activator agglomerateparticles of the present invention are derived from porous inorganicoxides including SiO₂, Al₂O₃, AlPO₄, MgO, TiO₂, ZrO₂; mixed inorganicoxides including SiO₂.Al₂O₃, MgO.SiO₂.Al₂O₃, SiO₂.TiO₂.Al₂O₃,SiO₂.Cr₂O₃.TiO₂ and SiO₂.Cr₂O₃.TiO₂ based on the weight of the catalystsupport. Where the inorganic oxide (including mixed inorganic oxides) iscapable of forming a gel by known commercial procedures, it is preferredto utilize the same in a gel configuration for the milling proceduresdescribed herein. If the inorganic oxide is not susceptible to gelformation, the free oxide or mixed oxides derived from otherconventional techniques such as precipitation, coprecipitation, or justadmixing, can be utilized directly for the milling procedures afterwashing.

Most preferably, Component-A of the support-activator contains typicallyat least 80, preferably at least 90, and most preferably at least 95%,by weight, silica gel (e.g., hydrogel, aerogel, or xerogel) based on theweight of the catalyst support.

Silica hydrogel, also known as silica aquagel, is a silica gel formed inwater which has its pores filled with water. A xerogel is a hydrogelwith the water removed. An aerogel is a type of xerogel from which theliquid has been removed in such a way as to minimize any collapse orchange in the structure as the water is removed.

Silica gel is prepared by conventional means such as by mixing anaqueous solution of an alkali metal silicate (e.g., sodium silicate)with a strong acid such as nitric or sulfuric acid, the mixing beingdone under suitable conditions of agitation to form a clear silica solwhich sets into a hydrogel in less than about one-half hour. Theresulting gel is then washed. The concentration of the SiO₂ in thehydrogel which is formed is usually in the range of typically betweenabout 15 and about 40, preferably between about 20 and about 35, andmost preferably between about 30 and about 35 weight percent, with thepH of that gel being from about 1 to about 9, preferably 1 to about 4. Awide range of mixing temperatures can be employed, this range beingtypically from about 20 to about 5° C.

Washing is accomplished simply by immersing the newly formed hydrogel ina continuously moving stream of water which leaches out the undesirablesalts, leaving about 99.5 wt. % pure silica (SiO₂) behind.

The pH, temperature, and duration of the wash water will influence thephysical properties of the silica, such as surface area (SA) and porevolume (PV). Silica gel washed at 65-90° C. at pH's of 8-9 for 28-36hours will usually have SA's of 290-350 m²/g and form aerogels with PV'sof 1.4 to 1.7 cc/gm. Silica gel washed at pH's of 3-5 at 50-65° C. for15-25 hours will have SA's of 700-850 m²/g and form aerogels with PV'sof 0.6-1.3 cc/g

When employing a Component-A inorganic oxide containing at least 80 wt.% silica gel, the remaining balance of the inorganic oxide Component-Acan comprise various additional components. These additional componentsmay be of two types, namely (1) those which are intimately incorporatedinto the gel structure upon formation, e.g., by cogelling silica gelwith one or more other gel forming inorganic oxide materials, and (2)those materials which are admixed with silica gel particles prior tomilling or after milling in slurry form just prior to spray drying.Thus, materials includable in the former category are silica-alumina,silica-titania, silica-titania-alumina, and silica-alumina phosphatecogels.

In the latter category, components which may be admixed, in slightproportions, with the silica hydrogel particles prior to milling and/orjust prior to agglomeration include those prepared separately frominorganic oxides such as magnesium oxide, titanium oxide, thorium oxide,e.g., oxides of Groups 4 and 16, as well as other particulateconstituents.

Other particulate constituents which may be present include thoseconstituents having catalytic properties, not adversely affected bywater, spray drying or calcination, such as finely divided oxides orchemical compounds, recognizing, however, that these constituents playno part in the agglomeration procedure. Similarly, it is possible to addpowders or particles of other constituents to the silica hydrogelparticles to impart additional properties to the support-activatorobtained. Accordingly, in addition to those powders or particulateshaving catalytic properties, there may be added materials which possessabsorbent properties, such as synthetic zeolites.

Thus, it is possible to obtain complex catalyst supports whereinamorphous silica gel contains crystallizable elements and the like. Theskilled artisan will appreciate that the amounts of such additionalcomponents must be restricted in order to avoid compromising the desiredagglomerate properties described herein.

Also, it is feasible to add constituents to the inorganic oxide whichmay be eliminated after agglomeration in order to control porositywithin a desired range; such agents as sulfur, graphite, wood charcoal,and the like being particularly useful for this purpose.

When non-silica gel components are to be employed with silica gel, theymay be added to the slurry to be agglomerated. However, it is preferablethat they be present in the silica gel during or prior to milling asdescribed hereinafter, since they will be less likely to disturb thedesired agglomerate morphology after spray drying when they are alsosubjected to milling.

In view of the above, the term “silica gel”, when used to describe theprocess steps up to and including agglomeration, is intended to includethe optional inclusion of the aforementioned non-silica gel constituentspermitted to be present in Component-A of the support-activator.

Component-B of the support-activator is a layered material having athree-dimensional structure which exhibits the strongest chemical bondsin only two dimensions. More specifically, the strongest chemical bondsare formed in and within two dimensional planes which are stacked on topof each other to form a three dimensional solid. The two dimensionalplanes are held together by weaker chemical bonds than those holding anindividual plane together and generally arise from Van der Waals forces,electrostatic interactions, and hydrogen bonding. The electrostaticinteractions are mediated by ions located between the layers and inaddition, hydrogen bonding can occur between complimentary layers or canbe mediated by interlamellar bridging molecules.

Representative examples of suitable layered materials includable inlayered Component-B can be amorphous or crystalline, preferablyamorphous. Suitable layered Component-B materials include clay, and clayminerals.

Clay is typically composed of clay minerals (i.e., crystalline silicatesalts) as the main constituent. The clay or clay mineral is usually aninorganic polymeric compound of high molecular complexity constituted bya tetrahedral unit in which a central silicon atom coordinates oxygenatoms and an octahedral unit in which a central aluminum, magnesium oriron atom coordinates oxygen or hydroxide. The skeletal structures ofmany clays or clay minerals are not electrically neutral and havepositive, most typically negative, charges on their surfaces. Whenpossessing a negatively charged surface, they have cations in theirinterlaminar structures to complement such negative charges. Suchinterlaminar cations can be ion-exchanged by other cations. Aquantification of a clay's ability to exchange interlaminar cations iscalled its cation exchange capacity (CEC) and is represented bymilliequivalents (meq) per 100 g of clay. CEC differs depending upon thetype of clay, and Clay Handbook, second edition (compiled by JapaneseClay Association, published by Gihodo Shuppan K.K.) gives the followinginformation. Kaolinite: 3 to 15 meq/100 g, halloysite: 5 to 40 meq/100g, montmorillonite: 80 to 150 meq/100 g, illite: 10 to 40 meq/100 g,vermiculite: 100 to 150 meq/100 g, chlorite; 10 to 40 meq/100 g,zeolite. attapulgite: 20 to 30 meq/100 g. Thus, layered Component-B tobe used in the present invention, is a material, e.g., clay or claymineral, typically having its surface negatively charged and preferablyalso having the ability to exchange cations.

Thus, clay minerals generally have the characteristic layer structuredescribed above, containing between the layers, various levels ofnegative charges. In this respect, the clay mineral is substantiallydifferent from metal oxides having a three-dimensional structure such assilica, alumina, and zeolite. The clay minerals are classified accordingto the levels of the aforementioned negative charge for the chemicalformula: (1) biophilite, kaolinite, dickalite, and talc having thenegative charge of 0 (zero), (2) smectite having the negative charge offrom −0.25 to −0.6, (3) vermiculite having the negative charge of from−0.6 to −0.9, (4) mica having the negative charge of from about −1, and(5) brittle mica having a negative charge of about −2. Each of the abovegroups includes various minerals. For example, the smectite groupincludes montmorillonite, beidellite, saponite, nontronite hectorite,teniolite, suconite and related analogues; the mica group includes whitemica, palagonite and illite. These clay minerals exist in nature, andalso can be synthesized artificially with a higher purity.

Any of the natural and artificial clay minerals having a negative chargebelow 0 are useful in the present invention. The presently preferredclay is montmorillonite, e.g., sodium montmorillonite.

Further, clays and clay minerals may be used as they are withoutsubjecting them to any treatment prior to formation of thesupport-activator therefrom, or they may be treated by ball milling,sieving, acid treatment or the like prior to such formation. Further,they may be treated to have water added and adsorbed or may be treatedfor dehydration under heating before support-activator formation. Theymay be used alone or in combination as a mixture of two or more of themfor support-activation synthesis.

Component-B preferably has a pore volume of pores having a diameter ofat least 40 Å (e.g., 40-1000 Å) as measured by a mercury intrusionmethod employing a mercury porosimeter of at least 0.1 cc/g, morepreferably from 0.1 to 1 cc/g. The average particle size of Component-Bcan vary typically from about 0.01 to about 50, preferably from about0.1 to about 25, and most preferably from about 0.5 to about 10 microns.

The clays suitable for use as Component-B of the support-activator maybe subjected to pretreatment with chemicals prior or subsequent tosupport-activator formation. Examples of the chemical pretreatmentinclude treatment with an acid or alkali, treatment with a salt, andtreatment with an organic or inorganic compound. The last treatment canresult in formation of a composite material.

The treatment of the clay mineral with the acid or alkali may not onlyremove impurities from the mineral, but also may elute part of metalliccations from the crystalline structure of the clay, or may destructivelyalter the crystalline structure into an amorphous structure.

Examples of the acids used for this purpose are Brønstead acids, such ashydrochloric, sulfuric, nitric, acetic acid and the like.

Sodium hydroxide, potassium hydroxide and calcium hydroxide arepreferably used as alkali chemical in the alkali pretreatment of theclay mineral.

In the case where the clay mineral is pretreated with a salt or aninorganic, or organic compound to give a composite material, thecrystalline structure may be retained substantially without being brokenand, rather a product that has been modified by ion-exchange may beobtained.

Examples of the inorganic salt compounds that may be used in thepretreatment with salts include ionic halide salts, such as sodiumchloride, potassium chloride, lithium chloride, magnesium chloride,aluminum chloride, iron chloride and ammonium chloride; sulfate salts,such as sodium sulfate, potassium sulfate, aluminum sulfate and ammoniumsulfate; carbonate salts, such as potassium carbonate, sodium carbonateand calcium carbonate; and phosphate salts, such as sodium phosphate,potassium phosphate, aluminum phosphate and ammonium phosphate. Examplesof the organic salt compounds include sodium acetate, potassium acetate,potassium oxalate, sodium citrate, sodium tartarate and the like.

In the case where the clay mineral is treated with an organic compound,such compounds will typically comprise a Lewis basic functional groupcontaining an element of the Group 15 or 16 of the Periodic Table, suchas organoammonium cation, oxonium cation, sulfonium cation, andphosphonium cation. The organic compound may also preferably comprise afunctional group other than the Lewis basic functional group, such ascarbonium cation, tropylium cation, and a metal cation. After undergoingsuch treatment, the exchangeable metallic cations originally present inthe clay mineral are exchanged with the enumerated organic cations.Thus, compounds that yield a carbon cation, for example, tritylchloride, tropylium bromide and the like; or a complex compound thatyields metallic complex cation, for example a ferrocenium salt and thelike; may be used as the organic compound in the pretreatment. Inaddition to these compounds, onium salts may be used for the samepurpose.

As examples of the inorganic compound used for the synthesis ofinorganic composite material, metal hydroxides that yield hydroxideanions, for example, aluminum hydroxide, zirconium hydroxide, chromiumhydroxide and the like may be mentioned.

Particular examples of guest organic cations that may be introduced formodification of the clay minerals, include: triphenylsulfonium,trimethylsulfonium, tetraphenylphosphonium, alkyl tri(o-tolyl)phosphonium, triphenylcarbonium, cycloheptatrienium, and ferrocenium;ammonium ions, for example aliphatic ammonium cations, such as butylammonium, hexyl ammonium, decyl ammonium, dodecyl ammonium, diamylammonium, tributyl ammonium, and N,N-dimethyl decyl ammonium; andaromatic ammonium cations such as anilinium, N-methyl anilinium,N,N-dimethyl anilinium, N-ethyl anilinium, N,N-diethyl anilinium, benzylammonium, toluidinium, dibenzyl ammonium, tribenzyl ammonium,N,N-2,4,6-pentamethyl anilinium and the like; and also oxonium ions,such as dimethyl oxonium, diethyl oxonium and the like. These examplesare not limiting.

Ion exchange of the exchangeable cations in the clay mineral withselected organic cations is typically brought about by contacting theclay with an onium compound (salt) comprising the organic cations.

Particular examples of the onium salts which may be used, include:ammonium compounds; for example aliphatic amine hydrochloride salts,such as propylamine HCl salt, isopropylamine HCl salt, butylamine HClsalt, hexylamine HCl salt, decylamine HCl salt, dodecylamine HCl salt,diamylamine HCl salt, tributylamine HCl salt, triamylamine HCl salt,N,N-dimethyl decylamine HCl salt, N,N-dimethyl undecylamine HCl salt andthe like; aromatic amine hydrochloride salts, such as aniline HCl salt,N-methylaniline HCl salt, N,N-dimethylaniline HCl salt, N-ethylanilineHCl salt, N,N-diethylaniline HCl salt, o-toluidine HCl salt, p-toluidineHCl salt, N-methyl-o-toluidine HCl salt, N-methyl-p-toluidine HCl salt,N,N-dimethyl-o-toluidine HCl salt, N,N-dimethyl-p-toluidine HCl salt,benzylamine HCl salt, dibenzylamine HCl salt, N,N-2,4,6-pentamethylaniline HCl salt and the like; hydrofluoric, hydrobromic and hydroiodicacid salts and sulfate salts of the above-listed aliphatic and aromaticamines; and oxonium compounds, such as hydrochloric acid salts of methylether, ethyl ether, phenyl ether and the like. Of the onionium compoundsthe exemplified ammonium or oxonium compounds, preferably the ammoniumcompounds and more preferably the aromatic amine salts are employed inthe modification of the clay mineral.

The onium compound to be reacted with the clay mineral may be in theisolated form. Alternatively, the onium compound may be formed in situ,for example by contacting the corresponding amine compound, aheteroatom-containing compound, such as an ether or sulfide compound,and a proton acid, such as hydrofluoric, hydrochloric, hydroiodic orsulfuric acid, in the reaction solvent in which the clay mineral is tobe pretreated subsequently. The reaction conditions under which the claymineral can be modified by the onium compound are not critical. Also therelative proportions of the reactants used therein are not critical.Preferably, however, when used the onium compound is employed in aproportion of not less than 0.5 equivalents per equivalent of the cationpresent in the clay mineral, and more preferably in a proportion of atleast equivalent amount. The clay mineral may be used singly or inadmixture with other clay mineral or minerals. Also the onium compoundmay be used singly or in admixture with other onium compounds. Thereaction solvent used in the modification pretreatment process may bewater or a polar organic solvent. Examples of the organic solvents whichmay be used suitably, include alcohols, such as methyl alcohol, ethylalcohol and the like; acetone, tetrahydrofuran, N,N-dimethyl formamide,dimethylsulfoxide, methylene chloride and the like. The solvent may beused singly or as a mixture of two or more solvents. Preferably, wateror an alcohol is employed.

What can be viewed as separate and distinct classes of chemicalmodification treatments to which the clays can be subjected is referredto as pillaring and delamination. Pillaring is a phenomena whereby theplatelets of certain clays, such as smectite clays, which are swellable,are separated by intercalation of large guest cations between thenegatively charged platelet sheets, which cations function as molecularprops or pillars separating the platelets and preventing the layers fromcollapsing under van der Waals forces.

Pillared clays are typically prepared by reacting a smectite clay, suchas montmorillonite, with polyoxymetal cations such as polyoxycations ofaluminum and zirconium. The reaction product is normally dried in airand calcined to convert the intercalated cations into metal oxideclusters interposed between the platelets of the clay such that thespacing between the platelets ranges from about 6 to about 10 Angstromsand is maintained at such values when the clay is heated to atemperature between about 500° C. and 700° C. When the reaction productis dried, the clay platelets, which are propped apart by the metal oxideclusters, orient themselves face-to-face, thereby forming a lamellarstructure which yields an X-ray diffraction pattern containing distinctfirst order or (001) reflection. The extent of lamellar ordering isindicated by the X-ray powder diffraction pattern of the pillared clay.A well-ordered, air-dried, pillared montmorillonite may exhibit six ormore orders of reflection. Pillared clays and their preparation aredescribed more fully in the article entitled “Intercalated ClayCatalysts,” Science, Vol. 220, No. 4595 pp. 365-371 (Apr. 22, 1983) andin U.S. Pat. Nos. 4,176,090; 4,216,188; 4,238,364; 4,248,739; 4,271,043;4,367,163; 4,629,712; 4,637,992; 4,761,391; 4,859,648; and 4,995,964.The disclosures of the aforementioned articles and patents areincorporated herein by reference in their entireties.

In contrast to pillared clays, having platelets which are ordered in aface-to-face arrangement, delaminated clays also contain large cationsbut the platelets are oriented edge-to-edge and edge-to-face in what canbe described as a “house-of-cards” structure containing macropores of asize typically found in amorphous aluminosilicates in addition to themicropores found in pillared clays. (See U.S. Pat. No. 4,761,391 for afurther discussion.)

Accordingly, it is contemplated that such pillared and delaminated claysare includable as further embodiments of modified clays which may beemployed as Component-B in the support activator.

While it is possible and permissible to modify Component-B with guestcations as described above, such procedures add process steps to theoverall preparation, and from a process point of view, are preferablynot employed.

However, when Component-B is modified by exchanging originally presentcations for guest cations, the goal sought to be achieved by suchexchange is to render the support-activator capable of activating eitherthe pre-catalyst or the pre-activated catalyst as described above. It isbelieved that the indigenous cations typically present in theaforementioned clays are already capable of accomplishing this goal.

The support-activator is made from an intimate admixture of Components-Aand -B, which admixture is shaped in the form of an agglomerate.

The weight ratio of Components-A:-B in the agglomerate can varytypically from about 0.25:1 to about 99:1, preferably from about 0.5:1to about 20:1, most preferably from about 1:1 to about 10:1 (e.g., 4:1).

The term “agglomerate” refers to a product that combines particles whichare held together by a variety of physical-chemical forces.

More specifically, each agglomerate is preferably composed of aplurality of contiguous, constituent primary particles derived primarilyfrom Component-A and much smaller secondary constituent particlesderived from both Component-A and Component-B preferably joined andconnected at their points of contact.

The agglomerates of the present invention preferably will exhibit ahigher macropore content than the constituent primary or secondaryparticles as a result of the interparticle voids between the constituentparticles. However, such interparticle voids may be almost completelyfilled with the smaller secondary particles in other embodiments of thespray dried agglomerates.

The agglomeration of Components-A and -B may be carried out inaccordance with the methods well known to the art, in particular, bysuch methods as pelletizing, extrusion, shaping into beads in a rotatingcoating drum, and the like. The nodulizing technique whereby compositeparticles having a diameter of not greater than about 0.1 mm areagglomerated to particles with a diameter of at least about 1 mm bymeans of a granulation liquid may also be employed.

However, the preferred agglomerates are made by drying, preferably spraydrying a slurry of Components-A and -B.

More specifically, in this embodiment, the support-activator is made byadmixing Components-A and -B to form a slurry, preferably an aqueousslurry, comprising typically at least 50, preferably at least 75 (e.g.,at least 80), and most preferably at least 85 (e.g., at least 90), wt. %water based on the slurry weight. However, organic solvents, such as C₅to C₁₂ alkanes, alcohols (e.g. isopropyl alcohol), may also be employedalthough they represent a fire hazard relative to water and often makeagglomerates too fragile for use as polymerization catalysts.

To render Component-A suitable for agglomerate formation, e.g. drying orspray drying, various milling procedures are typically employed. Thegoal of the milling procedure is to ultimately provide Component-A, whenintended to be spray dried, with an average particle size of typicallyfrom about 2 to about 10 (e.g. 3 to about 7) preferably from about 4 toabout 9, and most preferably from 4 to 7 microns. Desirably the millingprocedures will also impart a particle size Distribution Span to theparticles in the slurry of typically from 0.5 to about 3.0, andpreferably from about 0.5 to about 2.0. The particle size DistributionSpan is determined in accordance with the following equation.$\begin{matrix}{{{Distribution}\quad {Span}} = \frac{D_{90} - D_{10}}{D_{50}}} & \text{Equation~~1a}\end{matrix}$

wherein D₁₀, D₅₀, and D₉₀ represent the 10^(th), 50^(th), and 90^(th)percentile, respectively, of the particle size (diameter) distribution,i.e. a D₉₀ of 100 microns means that 90 volume % of the particles havediameters less than or equal to 100 microns. Still more preferably, themilling is conducted to impart a particle size distribution to theComponent-A inorganic oxides in the slurry to be spray dried such thatthe Component-A colloidal content is typically from about 2 to about 60(e.g. 2 to about 40), preferably from about 3 to about 25, and mostpreferably from about 4 to about 20 wt. %.

The colloidal content of Component-A to be spray dried is determined bycentrifuging a sample for 30 minutes at 3600 RPM. The liquid(supernatant) which remains on top of the test tube is decanted, andanalyzed for % solids. The % of colloidal material is then determined bythe following equation: $\begin{matrix}{{\% \quad {colloid}} = {\lbrack \frac{( \frac{1 - B}{B} ) - 2.2}{( \frac{1 - A}{A} ) - 2.2} \rbrack*100}} & \text{Equation~~1b}\end{matrix}$

wherein

A=wt. % solids in supernatant/100, and

B=wt. % solids of original slurry/100

The colloidal content will possess a particle diameter in the colloidalrange of typically less than about 1, preferably less than about 0.5,and typically from about 0.4 to about 1 micron.

All particle size and particle size distribution measurements describedherein are determined by a Mastersizer unit from Malvern, which operateson the principle of laser light diffraction and is known to all familiarin the art of small particle analysis.

As the colloidal content of the dry solids content of the Component-Aslurry exceeds about 60 wt. %, the constituent particles of theagglomerate can become bound too tightly together.

Conversely, while the presence of at least some colloidal content of theslurry is desired, a slurry containing no colloidal content (e.g. drymilled powder alone) will typically produce agglomerates of thesupport-activator which have extremely low physical integrity to anundesirable degree and typically will be undesirable as a support for apolymerization catalyst without some alternative source of binder.

One milling procedure which has been found to impart the aforedescribedproperties, as well as the desired morphology, involves a wet millingprocedure and optionally a dry milling procedure.

A wet milling procedure is characterized by the presence of liquid, e.g.water, during the milling procedure. Thus, wet milling is typicallyperformed on a slurry of the inorganic oxide particles having a solidscontent of typically from about 15 to about 25 weight % based on theslurry weight.

More specifically, with wet milling, Component-A is slurried in a media(usually water) and the mixture then subjected to intense mechanicalaction, such as the high speed blades of a hammer mill or rapidlychurning media of a sand mill. Wet milling reduces particle size andproduces colloidal silica as well.

A dry milling procedure is characterized by the substantial absence ofthe presence of free flowing liquid, e.g. water or solvent. Thus, whilethe final dry milled material may contain some absorbed moisture, it isessentially in powder form, not a suspension or solution of particles inliquid.

The dry milling referred to typically takes particulate inorganic oxideand reduces it in size either by mechanical action, impingement onto ametal surface, or collision with other particles after entrainment intoa high-velocity air stream.

Accordingly, the inorganic oxide (typically while still wet) is thensubjected to a milling operation as described below to prepare it forspray drying.

In the wet milling procedure, the washed inorganic oxide is typicallysubjected to a milling procedure well known in the art that is necessaryto produce slurries with the particle sizes specified above. Suitablemills include hammer mills, impact mills (where particle sizereduction/control) is achieved by impact of the oxide with metal bladesand retained by an appropriately sized screen), and sand mills (whereparticle size control/reduction is achieved by contact of the oxide withhard media such as sand or zirconia beads).

The colloidal particles within the wet milled material are the primarysource of the colloid content in the slurry to be spray dried asdescribed above, and are believed to act as a binder upon spray drying.

In the dry milling procedure, Component-A is typically milled in amanner sufficient to reduce its average particle size to typically fromabout 2 to about 10, preferably from about 3 to about 7, and mostpreferably from about 3 to 6 microns, and its moisture content totypically less that about 50, preferably less than about 25, and mostpreferably less that about 15 weight %. In order to attain the drymilling particle size targets at the higher moisture contents, it may benecessary to conduct dry milling while the particles are frozen.

The dry milling is also conducted to preferably impart a particle sizedistribution such that the Distribution Span is typically from about 0.5to about 3.0, preferably from about 0.5 to about 2.0, and mostpreferably from about 0.7 to about 1.3.

Thus, the resulting dry milled material exists in the form of a powderprior to being slurried for spray drying.

The dry milling is preferably conducted in a mill capable of flashdrying the inorganic oxide while milling. Flash drying is a standardindustrial process where the material to be dried is quickly dispersedinto a hot air chamber and exposed to an air stream of 370-537° C. Therate of air and material input is balanced such that the temperature ofthe outgoing air and the material entrained in it is generally 121-176°C. The whole process of drying usually takes place in less than 10seconds, reducing the moisture content to less than about 10%.Alternatively, the inorganic oxide can be separately flash dried to theaforedescribed moisture content in a flash dryer and then placed in adry mill and milled. Suitable dry mills include an ABB Raymond™ impactmill or an ALJET™ FLUID ENERGY MILL. Ball mills can also be used.Suitable flash drying equipment includes Bowen™ flash dryer. Othersimilar equipment is well known in the chemical processing industry.

Flash drying is typically accomplished by exposing the inorganic oxideto conditions of temperature and pressure sufficient to reduce themoisture content thereof to levels as described above over a period oftime of typically less than about 60, preferably less than about 30, andmost preferably less than about 5 seconds.

Dry milling typically does not produce colloidal silica.

In accordance with one embodiment of the agglomerate formation by spraydrying, at least a portion of the material constituting Component-A isderived from wet milling, and optionally but preferably at least aportion is derived from dry milling. Thus, prior to agglomeration,Component-A will typically comprise a mixture of previously wet milledinorganic oxide, e.g. silica gel, and dry milled inorganic oxide, e.g.silica gel powder. More specifically, the weight ratio (on a dry solidscontent basis as defined hereinafter) of the wet milled:dry milledinorganic oxide solids in the slurry can vary typically from about 9:0to about 0.1:1 (e.g., 9:1), preferably from about 1.5:1 to about 0.1:1,and most preferably from about 0.6:1 to about 0.25:1.

The particular wet milled:dry milled solids ratio of Component-Aemployed will be selected to achieve the target properties in the finalslurry to be used in agglomerate formation.

In an alternative embodiment, a sequential milling procedure can beemployed to impart the target properties of average particle size andparticle size distribution. The sequential milling procedure involvesdry milling a sample of the Component-A inorganic oxide and then wetmilling the previously dry milled sample.

It has been observed that drying of inorganic oxide starting materialduring dry milling and then using the dry milled product for wet millingtends to produce a lower colloidal content relative to mixing aseparately prepared dry milled product and a separately prepared wetmilled product. The reason for this phenomenon is not entirelyunderstood. However, sufficient colloidal content is produced to bindthe agglomerate together in a desirable manner.

Once the target average particle size and preferably the particle sizeDistribution Span is imparted to Component-A, a slurry, preferablyaqueous slurry, is prepared for agglomeration, preferably by spraydrying.

The Component-B layered material, e.g. clay, is typically comprised offine particles having an average particle size of typically less than10, preferably less than 5, and most preferably less than 1 micron, suchparticle sizes ranging typically from about 0.1 to about 10, preferablyfrom about 0.1 to about 5, and most preferably from about 0.1 to about 1microns.

Other preferable physical properties of the clay include a totalnitrogen pore volume of typically greater than 0.005 (e.g., 0.005 to1.50), preferably greater than about 0.1 (e.g., 0.1 to 2) cc/g; anitrogen surface area of typically greater than 10, preferably greaterthan 30 (e.g., 10 to 100) m²/g; and an Apparent Bulk Density (ABD) oftypically greater than 0.10, preferably greater than 0.25 (e.g., 0.10 to0.75) g/cc.

Milling procedures can be employed to achieve these target properties,if necessary.

To agglomerate by spray drying, Components-A and -B are admixed,typically in a suitable diluent, to form a slurry of the same. Thediluent can be aqueous or organic. The preferred liquid slurry mediumfor spray drying is aqueous, typically greater than 75, preferablygreater than 80, and most preferably greater than 95 wt. % water (e.g.entirely water).

The weight ratio of Component-A:Component-B in the slurry, can varytypically from about 0.25:1 to about 99:1, preferably from about 0.5:1to about 20:1, and most preferably from about 1:1 to about 10:1 (e.g.,4:1). The solids content of the slurry containing the mixture ofComponents-A and -B can vary typically from about 5 to about 25,preferably from about 10 to about 20, and most preferably from about 15to about 20 wt. % based on the slurry weight.

Accordingly, agglomerate formation is controlled to impart preferablythe following properties to the support-activator:

(1) A surface area of typically at least about 20, preferably at leastabout 30, and most preferably from at least about 50 m²/g, which surfacearea can range typically from about 20 to about 800, preferably fromabout 30 to about 700, and most preferably from about 50 to about 600m²/g;

(2) A bulk density of the support-activator particles of typically atleast about 0.15, preferably at least about 0.20, and most preferably atleast about 0.25 g/ml, which bulk density can range typically from about0.15 to about 1, preferably from about 0.20 to about 0.75, and mostpreferably from about 0.25 to about 0.45 g/ml;

(3) An average pore diameter of typically from about 30 to about 300,and most preferably from about 60 to about 150 Angstroms; and

(4) A total pore volume of typically from about 0.10 to about 2.0,preferably from about 0.5 to about 1.8, and most preferably from about0.8 to about 1.6 cc/g.

The particle size and particle size distribution sought to be impartedto the agglomerate support-activator particles is dictated andcontrolled by the type of polymerization reaction in which the ultimatesupported catalyst will be employed. For example, a solutionpolymerization process typically can employ an average particle size offrom about 1 to about 10 microns; a continuous stirred tank reactor(CSTR) slurry polymerization process of from about 8 to 50 microns; aloop slurry polymerization process of from about 10 to about 150microns; and a gas phase polymerization process of from about 20 toabout 120 microns. Moreover, each polymer manufacturer has its ownpreferences based on the particular reactor configuration.

Once the desired average particle size is determined for theagglomerates based on the targeted polymerization process, the particlesize distribution will desirably be such that the Distribution Span istypically from about 0.5 to about 4, preferably from about 0.5 to about3, and most preferably from about 0.5 to 2.

Accordingly, as a generalization, the average particle size of theagglomerates will range typically from about 4 to about 250 (e.g. about8 to about 200), and preferably from about 8 to about 100 (e.g. about 30to about 60) microns.

When the agglomerates are formed by spray drying, they can be furthercharacterized in that typically at least 80, preferably at least 90, andmost preferably at least 95 volume % of that fraction of the supportagglomerate particles smaller that the D₉₀ of the entire agglomerateparticle size distribution possesses microspheroidal shape (i.e.,morphology). Evaluation of the microspheroidal morphology is performedon that fraction of the particle size distribution of the supportagglomerates which is smaller than the D₉₀ to avoid distortion of theresults by a few large particle chunks which because of their largevolume, would constitute a non-representative sample of the agglomeratevolume. The term “spheroidal” as used herein means small particles of agenerally rounded, but not necessarily spherical shape. This term isintended to distinguish from irregular jagged chunks and leaf or rodlike configurations. “Spheroidal” is also intended to include polylobedconfigurations wherein the lobes are also generally rounded, althoughpolylobed structures are uncommon when the agglomerate is made asdescribed herein.

Each microspheroid is preferably composed of a loosely to densely packedcomposite of Components-A and -B typically with some, to substantiallyno, interstitial void spaces, and typically substantially no visibleboundaries, in an electron micrograph, between particles originallyderived from Components-A and -B.

However, microprobe image and elemental analysis of a cross-sectionedview of preferred agglomerate particles reveals that the Fe and Al ionsassociated with Component-B are distributed in clusters of varyingdensity around discrete sub-particles of material-bearing no iron oraluminum. This leads to the conclusion that, in the most preferredagglomerate particles, Component-B is intimately admixed withComponent-A such that islands of inorganic oxide (e.g., silica) aresurrounded by a matrix of inorganic oxide (most likely derived from thecolloidal constituents of the inorganic oxide) and layered material(e.g., clay). It is believed that the varying intensity (concentration)of Al and Fe, in the matrix is indicative of varying ratios ofComponent-A to Component-B in the matrix.

The microspherodial shape of the support-activator significantlyenhances the desired morphology of the polymers derived therefrom. Thus,one is able to simultaneously significantly enhance catalyst activityand desired polymer morphology by utilizing the 2 components ofsupport-activator.

The terms “surface area” and “pore volume” refer herein to the specificsurface area and pore volume determined by nitrogen adsorption using theB.E.T. technique as described by S. Brunauer, P. Emmett, and E. Tellerin Journal of American Chemical society, 60, pp. 209-319 (1939).

Bulk density is measured by quickly transferring (in 10 seconds) thesample powder into a graduated cylinder which overflows when exactly 100cc is reached. No further powder is added at this point. The rate ofpowder addition prevents settling within the cylinder. The weight of thepowder is divided by 100 cc to give the density.

Spray drying conditions are typically controlled in order to impart thedesired target properties described above to the agglomerate. The mostinfluential spray drying conditions are the pH of the aqueous slurry tobe spray dried, as well as its dry solids content. By “dry solidscontent” as used herein is meant the weight of solids in the slurryafter such solids have been dried at 175° C. for 3 hours, and then at955° C. for 1 hour. Thus, dry solids content is used to quantify theweight of solid ingredients which exist in the slurry and to avoidinclusion of adsorbed water in such weight.

Typically, the pH of the slurry will be controlled or adjusted to befrom about 5 to about 10 (e.g., 8 to 9), preferably from about 7 toabout 9, and the dry solids content will be controlled or adjusted to betypically from about 12 to 30, preferably from about 15 to about 25, andmost preferably from about 18 to about 22 (e.g. 20) weight % based onthe weight of the slurry and the dry weight of the gel.

Control of the remaining variables in the spray drying process, such asthe viscosity and temperature of the feed, surface tension of the feed,feed rate, the selection and operation of the atomizer (preferably anair atomizer is employed and preferably without the use of a pressurenozzle), the atomization energy applied, the manner in which air andspray are contacted, and the rate of drying, are well within the skillof the spray dry artisan once directed by the target properties soughtto be imparted to the product produced by the spray drying. (See forexample U.S. Pat. No. 4,131,452.)

Product separation from the drying air follows completion of the spraydrying stage when the dried product remains suspended in the air. Anyconvenient collection method can be employed, such as removal from thebase of the spray dryer by the use of separation equipment.

To provide uniformity to the catalyst as well as the resulting polymer,it is desirable to calcine the support-activator to control any residualmoisture present in the support.

When calcination is employed, it will typically be conducted atsufficient temperature and time to reduce the total volatiles to betweenabout 0.1 and 8 wt. % where the total volatiles are determined bymeasuring the weight loss upon destructive calcination of the sample at1000° C. However, the calcination temperature will also affect theinterrelationship between the desired silica:clay ratio and the orgnaoaluminum compound amount, and the activity of the catalyst as describedhereinafter in more detail. Accordingly, calcination, when employed,will typically be conducted by heating the support-activator totemperatures of typically from about 100 to about 800, preferably fromabout 150 to about 600, and most preferably from about 200 to about 300°C. for periods of typically from about 1 to about 600 (e.g., 50 to 600),and preferably from about 50 to about 300 minutes. The atmosphere ofcalcination can be air or an inert gas. Calcination should be conductedto avoid sintering.

After formation, the support-activator is preferably sized prior tocalcination since the agglomerates will pick up moisture if sized aftercalcination. This can be conveniently accomplished by screening or airclassifying as is well known in the art.

The particle size and particle size distribution selected will depend onthe catalyst type and polymerization process to be applied, as would bewell known in the art.

The preferred manner in which the support-activator is combined with thepre-catalyst will depend in part on the polymerization technique to beemployed.

More specifically, the catalyst system components described herein areuseful to produce polymers using high pressure polymerization, solutionpolymerization, slurry polymerization, or gas phase polymerizationtechniques. As used herein, the term polymerization includescopolymerization and terpolymerization, and the terms olefins andolefinic monomers include olefins, alpha-olefins, diolefins, styrenicmonomers, acetylenically unsaturated monomers, cyclic olefins, andmixtures thereof.

For example, polymerization of olefin monomers can be carried out in thegas phase by fluidizing, under polymerization conditions, a bedcomprising the target polyolefin powder and particulates of the catalystcomposition using a fluidizing gas stream comprising gaseous monomer. Ina solution process the (co)polymerization is typically conducted byintroducing the monomer into a solution or suspension of the catalystcomposition in a liquid hydrocarbon under conditions of temperature andpressure such that the produced polyolefin forms as a solution in thehydrocarbon diluent. In the slurry process, the temperature, pressureand choice of diluent are such that the produced polymer forms as asuspension in a liquid hydrocarbon diluent.

It will be apparent from the above discussion, that deployment of thecatalyst system can vary depending on the polymerization processemployed with a preference for permitting the formation in-situ of theactivated system in the presence of the polymerizable monomer.

Thus, for gas phase polymerizations, the pre-catalyst and optionally anorganometallic compound can be impregnated into the support-activatorwith a solvent and the solvent optionally evaporated, whereas forpolymerizations which occur in the liquid state the catalyst systemcomponents can be simply mixed in a hydrocarbon media for addition tothe polymerization zone, or to a media used as the liquid in which thepolymerizations are conducted.

As indicated above, an organometallic compound can be employed forpre-activation of the pre-catalyst, e.g., where L of the pre-catalyst ischlorine. It can also be employed as a scavenger for poisons in thepolymerization zone.

The mixing of pre-catalyst (referred to in the following discussion asComponent I), support-activator (referred to in the following discussionas Component II), and optionally organometallic compound (referred to inthe following discussion as Component III) can be readily accomplishedby introducing the components into a substantially inert (to chemicalreaction with Components I, II and III) liquid, which can serve as adiluent or solvent for one or more of the catalyst components.

More specifically, the inert liquid preferably is a non-solvent for theComponent II support-activator at contact temperatures to assure thatthe same will be suspended or dispersed in the liquid during contactwith Component I. The inert liquid can be a solvent for the Component Itransition metal compound.

Suitable inert liquids include hydrocarbon liquids, preferably C₅-C₁₀aliphatic or cycloaliphatic hydrocarbons, or C₆-C₁₂ aromatic or alkylsubstituted aromatic hydrocarbons and mixtures thereof.

The components are introduced into the liquid and maintained thereinunder agitation and at low temperature and pressure conditions.Particularly suitable hydrocarbons include, for example,1,2-dichloroethane, dichloromethane, pentane, isopentane, hexane,heptane, octane, isooctane, nonane, isononane, decane, cyclohexane,methylcyclohexane, toluene, and combinations of two or more of suchdiluents. Ethers such as diethylether and tetrahydrofuran can also beused.

The Components I, II and III can be introduced into the inert liquid inany order or substantially simultaneously. It is preferred that, whenthe components are introduced sequentially, they are introduced in rapidorder; that is, without a substantial period of delay between eachcomponents introduction. When sequential introduction is conducted, itis preferred that the components be added in the sequence of ComponentIII if employed, then Component II followed by Component I.

The temperature may range typically from about 0 to about 80, preferablyfrom about 5 to about 60, and most preferably from about 10 to about 40°C. (e.g., 15 to about 25° C.). The Components can be contacted atreduced, atmospheric or elevated pressure. Ambient conditions arepreferred. The atmospheric condition of the mixing zone shouldpreferably be substantially anaerobic and anhydrous.

The components are mixed for a period, preferably from 0.5 minute to1440 minutes (more preferably from 1 to 600 minutes), to provide asubstantially uniform mixed catalyst composition.

The formed mixture can be separated from the inert liquid, byfiltration, vacuum distillation or the like to provide a solid preformedcatalyst composition.

The solid preformed catalyst is preferably stored under anaerobicconditions until being introduced into a polymerization reaction zonefor use in forming polyolefin products. The resultant catalystcomposition is storage stable for about 3 to 6 months or longer.

Alternatively, the mixture of Components I, II and III in the inertliquid hydrocarbon, can remain without separation or purification as aslurry and be used directly as a polymerization catalyst composition.Thus, the present catalyst composition can be formed by the single-stepof mixing the readily available components in an inert liquid and theneither directly transferring the formed liquid dispersion to thepolymerization reaction zone or placing it in storage under anerobicconditions. In this embodiment, the inert liquid used to form thedispersion preferably is chosen from those liquids which (a) aremiscible with the liquids used in the polymerization reaction zone, (b)are inert with respect to the solvents, monomer(s) and polymer productscontemplated and (c) are capable of suspending or dispersing ComponentII (e.g., is a non-solvent for the support-activator).

The present polymerization catalyst composition can be formed in-situ ina liquid phase polymerization reaction zone. The organometallic compound(if employed) can be introduced neat or as a solution in an inertliquid, which may be the same liquid as that of the polymerizationmedia. The other components may be introduced into the polymerizationzone either as solids or as slurries in inert liquids. In all cases, theliquid(s) used to introduce the components forming the present catalystcomposition preferably is miscible with the liquid used as thepolymerization media.

A slurry of Components I, II and II can even be injected into a gasphase polymerization zone under conditions where the liquid slurrymedium desirably would be sprayed into the reaction zone whereby itwould desirably evaporate leaving the catalyst in a fluidized solidform.

In batch polymerization processes, the components forming the presentcatalyst composition may be introduced prior to, concurrently with orsubsequent to the introduction of the olefinic monomer feed. It has beenfound that the present catalyst composition forms rapidly under normalpolymerization conditions to exhibit high catalytic activity and providea high molecular weight polymer product.

The amount of Components I and II in the inert liquid hydrocarbon iscontrolled to be such as to provide a ratio of micromoles of Component I(pre-catalyst) to grams of Component II (support-activator) of typicallyfrom about 5:1 to about 500:1, preferably from about 10:1 to about250:1, and most preferably from about 30:1 to about 100:1 (e.g., 60:1).

The amount of optional organometallic compound in the inert liquidhydrocarbon depends on whether it is intended to be employed forpre-activation of the pre-catalyst or as a scavenger in thepolymerization zone. When employed for pre-activation it is controlledto be such as to provide a molar ratio of Component III (organometalliccompound to Component I (pre-catalyst) of typically from about 0.001:1to about 250:1, preferably from about 0.01:1 to about 125:1, and mostpreferably from about 0.1:1 to about 10:1. When employed as a scavengerby addition directly to the polymerization zone the molar ratio can varytypically from about 1:1 to about 1000:1, preferably from about 2:1 toabout 500:1, most preferably from about 10:1 to about 250:1.

Alternatively, one can express the amount of the organometalliccompound, when employed, as a function of the weight of thesupport-activator. More specifically, the ratio of millimoles (mmol) oforganometallic compound: grams of support-activator employed can varytypically from about 0.001:1 to about 2:1 (e.g., 0.05:1 to about 1:1),preferably from about 0.01:1 to about 1:1 (e.g., 0.01:1 to about 0.6:1),and most preferably from about 0.1:1 to about 0.8:1 (e.g., 0.1;1 toabout 0.5:1).

The amount of liquid hydrocarbon can vary typically from about 50 toabout 98, preferably from about 60 to about 98, and most preferably fromabout 75 to about 90 wt. % based on the combined weight of liquidhydrocarbon and Components I and II.

Without wishing to be bound to any particular theory, it is believedthat even without separation of the catalyst system from the inertliquid, the pre-catalyst and optional organometallic compound are veryquickly adsorbed (adhere to the surface of the support-activatoragglomerate) and/or absorbed (penetrate into the inner structure of thesupport-activator agglomerate particles) by the support-activator. It isbelieved that the pre-catalyst slowly reacts with the support-activatorthereby promoting the solubility of the pre-catalyst into the solutionphase and resulting in effective immobilization of the pre-catalyst ontothe support-activator matrix via mesoporous channels. This is believedto result in improved dispersion of pre-catalyst throughout theparticles.

More specifically, x-ray powder diffraction analysis of thesupport-activator impregnated with pre-catalyst displays an amorphousx-ray diffraction pattern wherein a sharp distinct peak originallypresent and attributable to pre-catalyst, has disappeared. Moreover,resolubilization of pre-catalyst was not observed when the catalystsystem was washed with CH₂Cl₂ (a known solvent which can dissolvepre-catalyst). When a blue solution of pre-catalyst in CH₂Cl₂ was mixedwith a tan slurry of support-activator in toluene, the color of thesupport-activator solid turned light blue while the supernatant CH₂Cl₂solution turned clear, further supporting the conclusion that some typeof reaction has taken place between the support-activator andpre-catalyst.

The organometallic compound, when employed during in-situ catalystformation, pre-activates the pre-catalyst which is then believed to befully activated by the Lewis acidity of the support-activator.

While the above discussion provides direction for controlling thesupport-activator calcination temperature, the Component-A (inorganicoxide):Component-B (layered material) wt. ratio, and the Component III(organometallic compound) content relative to either thesupport-activator weight or Component I pre-catalyst molar ratio, itwill be understood that it is desired to control such variables toimprove the catalyst activity relative to the activity of acorresponding catalyst system employing either Component-A alone orComponent-B alone.

The catalyst composition of the present invention can be used forpolymerization, typically addition polymerization, processes wherein oneor more monomers are contacted with the coordination catalyst system(either in its original inert liquid or as separated solid product, asdescribed above) by introduction into the polymerization zone underpolymerization conditions.

Suitable polymerizable monomers include ethylenically unsaturatedmonomers, acetylenic compounds, conjugated or non-conjugated dienes, andpolyenes. Preferred monomers include olefins, for example alpha-olefinshaving from 2 to 20,000, preferably from 2 to 20, and more preferablyfrom 2 to 8 carbon atoms and combinations of two or more of suchalpha-olefins. Particularly suitable alpha-olefins include, for example,ethylene, propylene, 1-butene, 1-pentene, 4-methylpentene-1,1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene or combinations thereof, aswell as long chain vinyl terminated oligomeric or polymeric reactionproducts formed during the polymerization and C₁₀₋₃₀ α-olefinsspecifically added to the reaction mixture in order to producerelatively long chain branches in the resulting polymers. Preferably,the alpha-olefins are ethylene, propene, 1-butene,4-methyl-pentene-1,1-hexene, 1-octene, and combinations of ethyleneand/or propene with one or more of such other alpha-olefins. The mostpreferred is ethylene alone or with other alpha-olefins. Other preferredmonomers include styrene, halo- or alkyl substituted styrenes,tetrafluoroethylene, vinylcyclobutene, 1,4-hexadiene, dicyclopentadiene,ethylidene norbornene, and 1,7-octadiene. Mixtures of theabove-mentioned monomers may also be employed.

In addition, the polymerization monomers may include functionalizedethylenically unsaturated monomers wherein the functional group isselected from hydroxyl, carboxylic acid, carboxylic acid esters,acetates, ethers, amides, amines and the like.

The present coordination catalyst system (composition) can beadvantageously employed in a high pressure, solution, slurry or gasphase polymerization process.

Methods and apparatus for effecting such polymerization reactions arewell known. The catalyst system according to the present invention canbe used in similar amounts and under similar conditions known for olefinpolymerization catalysts. Typically for the slurry process, thetemperature is from approximately 0° C. to just below the temperature atwhich the polymer becomes soluble in the polymerization medium. For thegas phase process, the temperature is from approximately 0° C. to justbelow the melting point of the polymer. For the solution process, thetemperature is typically the temperature from which the polymer issoluble in the reaction medium, up to approximately 275° C.

The pressure used can be selected from a relatively wide range ofsuitable pressures, e.g., from subatmospheric to about 20,000 psi.Preferred pressures can range from atmospheric to about 1000 psi, andmost preferred from 50 to 550 psi. In the slurry or particle formprocess, the process is suitably performed with a liquid inert diluentsuch as a saturated aliphatic hydrocarbon. The hydrocarbon is typicallya C₃ to C₁₀ hydrocarbon, e.g., propane, isobutane or an aromatichydrocarbon liquid such as benzene, toluene or xylene. The polymer canbe recovered directly from the gas phase process, by filtration orevaporation of the slurry from the slurry process, or evaporation ofsolvent in the solution process.

All references herein to elements or metals belonging to a certain Grouprefer to the Periodic Table of the Elements in Hawley's CondensedChemical Dictionary, 12^(th) Edition. Also, any references to the Groupor Groups shall be to the Group or Groups as reflected in this PeriodicTable of Elements using the new notation system for numbering groups.

The following examples are given as specific illustrations of theclaimed invention. It should be understood, however, that the inventionis not limited to the specific details set forth in the examples. Allparts and percentages in the examples, as well as in the remainder ofthe specification, are by weight unless otherwise specified.

Further, any range of numbers recited in the specification or claims,such as that representing a particular set of properties, units ofmeasure, conditions, physical states or percentages, is intended toliterally incorporate expressly herein by reference or otherwise, anynumber falling within such range, including any subset of numbers withinany range so recited.

EXAMPLE 1

Preparation of Support-Activator

Part A

Preparation of Base Silica Hydrogel

Silica gel is prepared by mixing an aqueous solution of sodium silicateand sulfuric acid under suitable agitation and temperature to form asilica sol that sets to a gel in about 8 minutes. The resulting gel isbase washed with dilute (about 2 wt. %) ammonia (NH₃) solution at 65.5°C. (150° F.) for 18 to 36 hours. During this time, the silica gel iscleansed of salt by-products and the surface area is modified. The basewash is followed by a fresh water wash wherein the gel is placed in arecirculating bath at 82° C.

The base washed gel was aged at 65-82° C. for about 36 hours and a pH of6 to 7 for one sample designated 1A, and a pH of 7.5 to 9 for anothersample designated 1B. The surface area of the gel is thereby reduced toabout 600 m²/g for Sample 1A and to 300 m²/g for Sample 1B. Theresulting water washed gel of Samples 1A and 1B have a SiO₂ content ofabout 35 wt. % with the balance being water, and an Average ParticleSize (APS) of Samples 1A and 1B from 0.5 to 2.0 cm.

Part B(i)

Preparation of Wet Milled Hydrogel Sample 2A (SA 600 m²/g)

A Sample 1A silica gel prepared in accordance with Part A was subjectedto wet milling in a sand mill. Sufficient water was then added theretoto make a slurry of 20 wt. % solids. The bulk sample particle size wasreduced with a blade mill and further processed through a wet sand millto reduce the average particle size (APS) to <100 microns. The samplewas then sand milled. The slurry was pumped through the sand mill at 1liter per minute with a media load of 80% (4 liters) zirconia silicate1.2 mm beads. The average particle size was reduced to 8 and 10 micronsand the particle size distribution was 4/8/15 microns for D10, D50 andD90. The surface area was 600 m²/g. The resulting wet milled sample wasdesignated Sample 2A. Sample 2A had a colloidal content between 20 and25 wt. % as determined by centrifugation.

Part B(ii)

Preparation of Wet Milled Hydrogel Sample 2B (SA 300 m²/g)

Example 1, Part B(i) was repeated using base silica gel Sample 1B. Theresulting wet milled sample was designated Sample 2B and had a colloidalcontent between 15 and 30 wt. % as determined by centrifugation and a SAof 300 m²/g. The resulting material was designated Sample 2B.

Part C

Preparation of Dry Milled Sample 3B (SA 300 m²/g)

A base silica gel Sample 1B prepared in accordance with Part A wassubjected to dry milling procedure as follows:

The sample was flash or spray dried to a moisture content below 10 wt.%. The dried powder sample was then milled to an average particle size(APS) of about 5 microns, a surface area (SA) of still about 300 m²/g,and a N₂ pore volume of 1.5 cc/g. The resulting sample was designatedSample 3B.

Part D

Preparations of Dry Milled Sample 3A (600 m²/g)

Part C was repeated except that the base silica gel was Sample 1Aprepared in accordance with Example 1, Part A. The resulting dry milledsample had a moisture content of less than 10 wt. %, an APS of 5 micronsand a SA of 600 m²/g. The resulting sample was designated Sample 3A.

Part E

Preparation of Silica Slurry

Seven different blends (designated Runs 1 to 6 and Run 9) of Sample 2Band Sample 3B were prepared at weight ratios of Sample 3B (drymilled):Sample 2B (wet milled) as reported in Table IV. Before blending,Sample 3B was slurried in water to a 20 wt. % solids content using amixer. The Sample 3B slurry was then added to the 20 wt. % solidscontent aqueous slurry of Sample 2B at amounts sufficient to achieve theratios reported in Table IV.

TABLE IV Silica Support Slurries Sample 3B (Dry Milled):Sample 2B (WetMilled) Run Ex or Comp Number Ex No. Weight % Ratio Weight Ratio 1 Ex 1Part E 79/21 3.75:1 2 Ex 1 Part E 78/22 3.50:1 3 Ex 1 Part E 75/253.00:1 4 Ex 1 Part E 70/30 2.25:1 5 Ex 1 Part E 60/40 1.50:1 6 Ex 1 PartE 0/100   0:1  7* Ex 2 70/30 0.43:1  8* Ex 3 100/0   0:1 9 Ex. 1, Part E80/20 0.25:1 *= tray dried

Part F

Preparation of Alternate Silica Support Slurries

Part E was repeated except that Sample 3B (300 m²/g) was replaced withSample 3A (600 m²/g) and Sample 2B (300 m²/g) was replaced with Sample2A (600 m²/g). The dry milled/wet milled ratios employed are summarizedat Table V and the slurries designated Runs 10 to 12.

TABLE V Sample 3A (Dry Milled):Sample 2A (Wet Milled) Run Number Weight% Ratio Weight Ratio 10 75/25 3.00:1 11 60/40 1.50:1 12 0/100   0:1

Part G

Preparation of Clay Slurry

A montmorillonite clay available from Southern Clay, under the tradenames, Montmorillonite BP Colloidal Clay, was obtained. This clay hasthe following properties as summarized at Table VI.

TABLE VI Chemical Composition of Montmorillonite BF Colloidal ClayComponent Weight % S_(i)O₂ 69.5 FE₂O₃ 4.4 Al₂O₃ 19.0 M_(g)O 2.3 C_(a)O1.0 Na₂O 2.7 SO₄ 0.6 Physical Properties Appearance Tan Powder ApparentBulk Density 0.45 g/cc Surface Area 70 m²/g APS 1.5 microns Average PoreDiameter 114 Å Total Pore Volume 0.20 cc/g

Part H

Preparation of Silica/Clay Slurry for Spray Drying

Each of the silica slurries of Runs 1 to 6 and 10 to 12 was combinedwith the clay slurry of Part G in a manner sufficient to control theweight ratio of silica:clay dry solids to be as reported at Table VII.Each slurry was adjusted with acid (sulfuric acid) or base (ammoniumhydroxide) to achieve a slurry pH of 7-8.5. The APS of the slurry solidswas about 4 to 5 microns, the total dry solids content of the slurry wasabout 15 to 18 wt. %. The resulting slurries are designated Runs 13 to21.

Part I

Spray Drying of Silica/Clay Slurry

Each pH adjusted slurry of Runs 13 to 21 was then pumped to a spraydryer to dry the mixture and to form microspheroidal agglomerates. Allspray drying is conducted by using a Bowen 3-ft. diameter spray dryerwith inlet-outlet temperatures of 350/150° C. and a two-fluid spraynozzle using air at 10-30 psi to atomize the slurry. The air through-putof the Niro is dampened to keep the spray chamber under 7″ water vacuumand the slurry is fed at 250-300 cc/min. The product is then collectedin the chamber collection pot, located directly under the dryingchamber, where the coarsest fraction drops out from air entrainment.Other, smaller fractions go to a cyclone collection pot and the smallestto a baghouse. The chamber material is then screened through 200 to 250mesh to give the desired APS of 40-55 microns. The Total Volatiles (TV%) at 954.4° C. (1750° F.) of the spray dried product is in the range of2-20 wt. %, so further drying in a static bed oven at 150-800° C. isthen used to lower the total volatiles down to 0.5-5%.

The total yield of material from the spray dryer chamber collection potand from screening the same is about 15-20 wt. %.

Table VIII below reports silica/clay morphological properties of theresulting agglomerates. The resulting Agglomerate Samples are designatedRuns 27 to 35.

EXAMPLE 2

(Tray Dried-Silica/Clay Support-Activator)

65 parts by weight of a silica sample (designated Run 7) prepared inaccordance with Example 1, Part E, but containing 30 wt. % wet milledsilica hydrogel Sample 2B (prepared in accordance with Example 1, PartB(ii) 300 m²/g) and 70 wt. % dry milled silica powder Sample 3B(prepared in accordance with Example 1, Part C (SA=300 m²/g)), weremixed with 35 parts by weight montmorillonite clay available under thetradename Mineral Colloidal BP from Southern Clay Company.

The mixture (designated Run 22) was made by adding the clay powder to a10% dry solids content slurry of the silica to bring the total solidscontent of clay plus silica to 15 wt. %. The slurry was then mixed.

At the solids content employed, the slurry existed as a paste which wasspread out on a tray to dry. The paste was then tray dried in a vacuumoven at 204.4° C. (400° F.) for 16 hours. The tray dried sample wascrushed and sieved through 200 U.S. mesh screen to yield an averageparticle size of about 50 microns. A portion of the sieved sample wastested for BET Surface Area and Nitrogen Pore Volume and found to be 215m²/g and 0.85 cc/g respectively. The resulting tray dried agglomeratesample was designated Run 36.

EXAMPLE 3

(Tray Dried Silica/Clay Support-Activator)

Example 2 was repeated except that the silica sample (designated Run 8)employed was entirely dry milled silica powder (no wet milled silicagel) prepared in accordance with Example 1, Part C.

The surface area and pore volume was analyzed and found to be 224 m²/g.and 0.82 cc/g respectively. The resulting tray dried sample wasdesignated Run 23.

Comparative Example 1

(Spray Dried 100% Clay)

5 parts-by-weight montmorillonite clay available from Southern ClayCompany under the tradename Mineral Colloidal BP was mixed with 28parts-by-weight water. The slurry (designated Run 24C) was the then fedto a Niro Spray Dryer in accordance with Example 1, Part I to make claymicrospheres. The resulting product never agglomerated intomicrospheroids. A very small quantity of material accumulated in thespray dryer chamber collection pot (<5% yield) and the remainder wasobserved as dust and build-up on the spray dryer wall. After screening,<1 wt. % of the collected sample was in the form of microspheroids withmost of the clay being carried over to the cyclone or baghouse as dust.The resulting spray dried clay, designated Run 38C, was unusable anddiscarded.

Comparative Example 2

(Spray Dried 100% Clay)

Comparative Example 1 was repeated except that the clay employed wasmontmorillonite available under the tradename Gel White from SouthernClay Products. The slurry to be spray dried is designated Run 25C. Only1.3 wt. % of the starting clay was recovered as agglomerates thataccumulated in the spray dryer chamber collection pot.

The crude agglomerated product was screen through 200 mesh screen toremove large agglomerates and give an APS of 40-55 microns (based onMalvern particle size analysis). This product has a pore volume of 0.21cc/g and the surface area is 72 m²/g.

The resulting spray dried clay powder was designated Run 39C.

Comparative Example 3

(100% Spray Dried Silica)

Example 1, Part I was repeated except that the slurry (designated Run26C) that was spray dried contained only silica, and the silica wasderived from Run 9, i.e., a mixture containing: 80 wt. % dry milledsilica powder Sample 3B and 20 wt. % wet milled silica hydrogel Sample2B. No clay was employed. The resulting spray dried product was amicrospheroidal agglomerate with a pore volume of 1.69 cc/g, a surfacearea of 277 m²/g and an average particle size (APS) of 47 microns. Theresulting spray dried product was designated Run 40C.

EXAMPLE 4

Preparation of Tridentate Catalyst System

The support-activators of Runs 27 to 34 were subjected to variouscalcination temperatures and times as indicated at Table IX to controlthe total volatiles thereof. Each designated calcined support-activatorwas then added to 25 ml of toluene along with sufficient tridentatetransition metal pre-catalyst, i.e., 2,6 bis (2,4,6-trimethylarylimino)pyridyl iron dichloride, to provide the ratio of micromoles ofpre-catalyst per gram of support-activator reported at Table IX Runs 41to 93 and 101 to 104. Triisobutyl aluminum (1M in toluene solution) wasalso added to the toluene in amounts sufficient to give the reportedmicromoles of triisobutylaluminum per gram of support-activator whenemployed.

Comparative Example 4

Example 4 was repeated two additional times and designated Runs 94C and95C except that the silica/clay support activator was replaced withcolloidal (<1 micron particle size) undehydrated and non-spray driedmontmorillonite available from Aldrich under the tradename K10Montmorillonite (Run 95C) and undehydrated non-spray dried MineralColloidal BP (Run 94C) (as described in Example 1, Part G). The ratiosof triisobutylaluminum and Fe-pre-catalyst are summarized at Table IX atRuns 95C and 94C respectively.

Comparative Example 5

Example 4 was repeated except that the silica-clay agglomerate wasreplaced with an unagglomerated physical blend of Mineral Colloidal (<1micron particle size) BP montmorillonite clay and silica hydrogel powder(Sample 4) prepared by the following procedure: A base silica hydrogelSample 1B (SA 300 m²/g) was wet milled to an APS of 15-25 microns toform a 20 wt. % solids slurry in water. The silica hydrogel was thenspray dried and the fraction of fines contained therein was collected byair classification and designated Sample 4. Sample 4 had an APS of 10microns, a Nitrogen pore volume of 1.6 cc/g and a surface area of 300m²/g. Pre-catalyst was then added in accordance with Example 4 and theresulting mixtures tested in accordance with Example 6 as Runs 96C and97C. The amounts of triisobutylaluminum and Fe-pre-catalyst ratios arereported at Table IX.

Comparative Example 6

Example 4 was repeated except that the Silica/Clay support activator wasreplaced with the silica agglomerate prepared in accordance with Run40C. The amounts of triisobutylaluminum and Fe-pre-catalyst are reportedat Runs 98C, 99C and 100C.

EXAMPLE 5

Example 4 was repeated except that the Silica/Clay support-activator wasreplaced with the tray dried samples of Runs 36 and 37 respectively. Theamounts and ratios of triisobutylaluminum and Fe-pre-catalyst employedare summarized at Table IX Runs 105 and 106.

EXAMPLE 6

Polymerization Method

In the slurry polymerization experiments of this Example, unlessotherwise indicated, a 2-liter Zipperclave (Autoclave Engineers, Inc.)reactor was rendered inert by heating under vacuum at 70° C. for 90minutes. A reactor charge consisting of a mixture of 350 ml of dry,degassed heptane and 200 micromoles of triisobutyl aluminum scavengerdissolved in toluene and, separately, 0.3 to 0.5 ml liters (depending oncatalyst activity) of a slurry of triisobutylaluminum, pre-catalyst andsupport-activator derived from one of Runs 41 to 106 of Table IX wereinjected into the reactor. While the reactor contents were stirred at500 rpm, ethylene and hydrogen were quickly admitted to the reactoruntil a final reactor pressure of 200 psig was attained. This pressurecomprised a hydrogen/ethylene partial pressure ratio of 0.05. Thepolymerization temperature was 70° C. which was maintained by acirculating water bath. Ethylene was supplied on demand via a mass flowcontroller to maintain the reactor pressure of 200 psig. After 60minutes, the ethylene feed was stopped and the reactor cooled to roomtemperature and vented. The polymer was filtered and washed withmethanol and acetone to deactivate any residual catalyst, filtered anddried in a vacuum oven for at least three hours to constant weight.After drying, the polymer was weighed to calculate catalyst activity anda sample of dried polymer was used to determine apparent bulk densityaccording to the procedure of ASTM 1895.

The results of each polymerization are summarized at Table IX Runs 41 to106. Column 7 depicts the amount (mmole) of triisobutylaluminum (AlBu₃)used with respect to the amount (grams) of support-activator materialduring the active catalyst preparation. Column 8 depicts the amount ofFe pre-catalyst and the amount (grams) of support-activator used duringthe active catalyst preparation. Column 11 depicts the bulk density ofthe resulting polyethylene (PE) product (determined by ASTM 1895method). The catalyst performance data include: (i) catalyst activitydata (Column 9) (KgPE/gCat-h) which is based on the total amount (grams)of polyethylene product produced per gram of total catalyst used perhour; and (ii) activity as a function of Fe concentration. Thus, Column10 represents gPE×10⁻⁶/gFe-h which is related to the total amount (gram)of polyethylene product produced per gram of Fe metal present in thepre-catalyst per hour. More specifically, a reported value of 1 inColumn 9 indicates 1,000,000 g of PE is produced per gram of Fe perhour. The particle size distributions of the resulting polymer particlesproduced by Runs 45, 56, 67 (spray dried support-activator), 105 and 106(tray dried support-activator), 94C (100% clay) and 96C(non-agglomerated physical mixture of silica and clay) are provided atTable X.

Discussion of Results

Comparing Runs 105 and 106 (tray dried) to Runs 62 to 65 (spray dried),it can be seen that spray dried agglomerates exhibit an activity between6.5 and 8 at AlBu₃ contents below 1 and between 5.5 and 8 for traydried. However, it is believed that because the tray driedsupport-agglomerates of Runs 105 and 106 are non-uniform in shape andsize, they produce a wide distribution in the polymer particle sizes(see Table X). In contrast, spray dried Runs 45, 56 and 67 produce nopolymer particles between 0 and 250 micron diameters. This reducespolymer fines and increases the ease with which the polymer can behandled. Similar considerations apply to the polymer of Run 94C whichemploys no silica and consequently was not spray dried because theproduct disintegrates into fines (see Run 38C). The resulting morphologyof this comparative clay-only support is believed to be responsible forthe poor polymer morphology.

Comparing Run 96C (80:20 silica:clay physical admixture) with Run 102(80:20 spray dried agglomerate), it can be seen that the activity of Run102 is almost 4 times greater than that of Run 96C. Thus, theconfiguration as an agglomerate is considered critical to the presentinvention relative to merely mixing silica particles with clay particlesin the polymerization zone or during activation. The physical blend ofsupport-activator components of Run 96C also yields a poor polymermorphology (see Table X Run 96C).

Comparing Runs 94C and 95C (100% clay) with Runs 41 to 45 (80:20silica:clay), it can be seen that very low activities (2.92 and 0respectively) are associated with a clay-only support versus activitiesof 5 to 10.3 for silica-clay support-activators.

Similar results are obtained by silica only support-activators. Forexample compare Runs 98C, 99C and 100C to Runs 101 to 104 wherein theactivities of the later are more than double those of the comparativeruns.

EXAMPLE 7

Cross Section Scanning Electron Micrograph (SEM)

A small portion of the sample from Run 30 was dispersed into an apoxyresin and allowed to cure overnight in a glove box containing Argon.Once the epoxy cured, the mounted sample was polished until the internalmatrix of several particles was exposed and a 0.05 um smooth surface wasachieved.

A small portion of the polished sample block was placed on a SEM stub ina glove box under Argon. Once the sample is mounted, it is placed into ajar in the glove box. The sealed jar containing the sample was thenplaced in a glove bag that has been placed over the opening of the SEMand is purged with Argon. Once the bag has been flushed with Argon threetimes, the sample jar is opened and the sample is placed into the SEMfor analysis. Images are obtained on the dry uncoated sample using aHitachi S4500 scanning electron microscope using a beam acceleratingvoltage of 1.0 kV. The results are shown at FIGS. 1 and 2.

EXAMPLE 8

Activity Response Contour Map

The data based on the 300 m²/g SA support-activator Samples 2B and 3Bfrom Table IX conducted in accordance with Example 6, were categorizedby their 4 hour calcination temperatures and subjected to aHyper-Greco-Latin Square (HGLS) experimental design algorithm. Fourvariables were examined, namely, (1) triisobutylaluminum loading, (2)wt. % clay in support-activator, (3) pre-catalyst loading, and (4)calcination temperature of support-activator. For each of thesevariables, a four-factor, four-level HGLS Design as shown by Table XIwas created. From the 34 available data points (16 from the design and18 extra data points, all reported at Table IX) and a 92% modelcoefficient, the average catalyst activities were then calculated inaccordance with the following equations:

Ln.(CA)=1.97260−1.03944*(AlBu₃−0.6)−0.00472*(Clay−45)−0.0014556*(Dry−370)−0.00023776*(Clay−45)*(Clay−45)−0.000003075*(Dry−370)*(Dry−370)−0.0019575*(AlBu₃−0.6)*(Dry−370)=0.00004975*(Clay−45)*(Dry−370)  Eq.2

and

Ln. Cat Activity=(e^(Ln.(CA)))−1  Eq. 3

wherein:

Ln.=natural log

Dry=4 hour support-activator Calcination Temperature ° C.

Clay=wt. % clay in support-activator

AlBu₃=m moles/g support-activator employed

These calculated activities were then employed to make the activitycontour maps of FIGS. 3 to 13.

The number on each line of each plot represents the catalyst activity,in units as described above, that would be expected at the illustratedcombination of wt. % clay and triisobutyl aluminum content.

Comparing FIGS. 3 to 14, it can be seen that catalyst activities as highas 13 can be achieved at very low AlBu₃ contents between 0.1 and 0.2 andclay contents in the support-activator between 20 and 30 wt. % when thesupport-activator is uncalcined or calcined up to 200° C. As thecalcination temperature increases from 250 to 800° C., the highestactivities drop below 13 and the clay content of the support-activatorcan be progressively increased in association with decreases in theAlBu₃ content and vice-versa to maintain a given activity. It will befurther observed that the activity consistently decreases as the AlBu₃content increases up to 1.

As a general proposition therefore, clay content in thesupport-activator and calcination temperature thereof are believed to bedirectly proportional to catalyst activity at increasingly highercalcination temperatures. However, the relationship between clay contentand activity becomes inversely proportional at a given calcinationtemperature. Also the AlBu₃ content is inversely proportional tocatalyst activity at all tested calcination temperatures at least up toa AlBu₃ content of 1. Moreover, clay content and AlBu₃ are generallyinversely proportional over a segment of a plot; e.g., at high. claycontents and directly proportional over another segment of the sameactivity plot. This transition from direct to inverse proportionality tomaintain a given activity occurs at higher clay contents for highercalcination temperatures.

EXAMPLE 9

Example 4 was repeated using the support-activator of Run 33 except thatthe reaction mixture of support-activator pre-catalyst and toluene wasagitated with an orbital shaker for 24 hours. The slurry was thenfiltered, washed two times with 20 ml toluene, two times with 20 ml ofheptane and dried in vacuo. The resulting powdered catalyst system wasthen employed for polymerization of ethylene in accordance with Example6 by reslurry of the powder into toluene prior to injection into thepolymerization reactor. The results are summarized at Run 107. Thepolymer product had a Mw of 358,100 an Mn of 37,600 and an Mw/Mn of 9.5.

TABLE VII Spray Drying or Tray Drying Slurry and Conditions Ex. No. orSource of Silica:Clay Comp. Ex Silica Dry Solids Run No. No. (Run Nos.)Ratio (w/w) 13 Ex 1 Pt H 1 95:5  14 Ex 1 Pt H 2 90:10 15 Ex 1 Pt H 380:20 16 Ex 1 Pt H 4 65:35 17 Ex 1 Pt H 5 50:50 18 Ex 1 Pt H 6 25:75 19Ex 1 Pt H 10 80:20 20 Ex 1 Pt H 11 50:50 21 Ex 1 Pt H 12 25:75 22 Ex 2 765:35 23 Ex 3 8 65:35 24C Comp Ex 1 none 0:1 25C Comp Ex 2 none 0:1 26CComp Ex 3 9 1:0

TABLE VIII Spray Dried Silica/Clay Support-Activator Product PropertiesColumn No. 2 3 4 5 6 7 1 Slurry Source Agglomerate Properties Ex. No. orfrom Table VII Silica/Clay APS SA Pore Vol. Drying Run No. Comp Ex. (RunNo.) (Weight Ratio) (microns) (m²/g) (cc/g) Procedure  27 Ex 1 13 95:5 45 275 1.65 Spray  28 Ex 1 14 90:10 45 268 1.61 Spray  29 Ex 1 15 80:2045 251 1.48 Spray  30 Ex 1 16 65:35 45 213 1.28 Spray  31 Ex 1 17 50:5045 185 1.04 Spray  32 Ex 1 18 25:75 45 160 0.64 Spray  *33 Ex 1 19 80:2045 494 1.16 Spray  *34 Ex 1 20 50:50 45 322 0.83 Spray  *35 Ex 1 2125:75 45 192 0.54 Spray  36 Ex 2 22 65:35 45 215 0.85 Tray  37 Ex 3 2365:35 45 224 0.82 Tray **38C Comp Ex 1   24C 0:1 N/A N/A N/A Spray  39CComp Ex 2   25C 0:1 40-55  72 0.21 Spray  40C Comp Ex 3   26C 1:0 47 2771.68 Spray *= Made from 600 m²/g silica **= Discarded APS = AverageParticle Size PSD = Particle Size Distribution based on D10, D50, D90percentile

TABLE IX 8 2 7 Fe Pre- 9 Support- 3 4 5 6 AlBu₃ Cat Cat 10 1 ActivatorCorresponding Silica:Clay Calcination mmol/g- μmol/g Activity FeActivity 11 Run Source Ex or Comp (Weight Temp Time Support- Support-KgPE/ gPE × 10⁻⁶/ B. D. No. (Run No.) Ex No. Ratio) ° C. (hr) ActivatorActivator gCat-h gFe-h g/cc  41 27 Ex 4 95:5  UC N/A 1 57.3 5.13 1.600.37  42 28 Ex 4 90:10 UC N/A 1 57.3 7.75 2.42 0.34  43 29 Ex 4 80:20 UCN/A 1 73.8 10.11 2.37 0.41  44 29 Ex 4 80:20 UC N/A 1 57.3 10.26 3.200.41  45 29 Ex 4 80:20 UC N/A 1.2 38.2 8.87 4.29 0.46  46 29 Ex 4 80:20150 4 0.4 76.3 7.86 1.84 0.42  47 29 Ex 4 80:20 250 4 1 57.3 0 0.00 NA 48 29 Ex 4 80:20 250 4 0.7 57.3 9.93 3.11 0.40  49 29 Ex 4 80:20 250 40.6 57.3 9.85 3.09 0.39  50 29 Ex 4 80:20 250 4 0.4 57.3 8.78 2.74 0.42 51 29 Ex 4 80:20 250 4 0.3 57.3 9.6 3.00 0.43  52 29 Ex 4 80:20 250 40.3 38.1 7.14 3.35 0.42  53 29 Ex 4 80:20 250 4 0.2 57.3 9.28 3.00 0.44 54 29 Ex 4 80:20 250 4 0.1 57.3 7 2.19 0.44  55 29 Ex 4 80:20 500 4 0.195.4 7.52 1.41 0.46  56 29 Ex 4 80:20 500 4 0.3 57.3 8.68 2.71 0.44  5729 Ex 4 80:20 800 4 0.1 57.3 1.72 0.54 NA  58 29 Ex 4 80:20 800 4 0.1257.3 2.35 0.73 0.29  59 29 Ex 4 80:20 800 4 0.8 57.3 0.04 0.01 NA  60 30Ex 4 65:35 UC N/A 0.5 57.3 9.7 3.03 0.34  61 30 Ex 4 65:35 UC N/A 0.495.4 8.54 1.60 0.38  62 30 Ex 4 65:35 450 4 1.2 57.3 1.66 0.78 NA  63 30Ex 4 65:35 150 4 0.6 57.3 6.7 2.10 0.38  64 30 Ex 4 65:35 450 4 0.3 57.37.1 2.22 0.41  65 30 Ex 4 65:35 150 4 0.12 57.3 7.73 2.42 0.43  66 30 Ex4 65:35 500 4 0.30 57.3 9.38 2.93 0.41  67 30 Ex 4 65:35 500 4 0.12 57.311.4 3.57 0.42  68 30 Ex 4 65:35 500 4 0.10 57.3 8.87 2.78 0.43  69 30Ex 4 65:35 500 4 0.08 57.3 5.27 1.65 0.41  70 30 Ex 4 65:35 500 4 0.8038.2 2.18 0.68 0.38  71 30 Ex 4 65:35 800 4 0.10 76.3 3.02 0.71 0.35  7231 Ex 4 50:50 UC N/A 0.1 57.3 8.51 2.66 0.37  73 31 Ex 4 50:50 150 4 0.257.3 6.48 2.00 0.40  74 31 Ex 4 50:50 150 4 0.3 57.3 7.52 2.35 0.38  7531 Ex 4 50:50 150 4 0.4 57.3 41.04 3.45 0.41  76 31 Ex 4 50:50 450 4 0.895.4 6.54 1.23 0.44  77 31 Ex 4 50:50 500 4 0.12 57.3 10.58 3.31 0.4  7831 Ex 4 50:50 500 4 0.1 57.3 6.53 2.04 0.38  79 31 Ex 4 50:50 500 4 1.276.3 1.44 0.27 NA  80 31 Ex 4 50:50 800 4 0.1 57.3 2.35 0.73 0.29  81 31Ex 4 50:50 800 4 0.4 38.2 2.06 0.97 0.31  82 32 Ex 4 25:75 UC N/A 0.857.3 1.45 0.45 NA  83 32 Ex 4 25:75 UC N/A 0.8 76.3 1.77 0.42 0.27  8432 Ex 4 25:75 UC N/A 1.2 57.3 2.77 0.87 0.34  85 32 Ex 4 25:75 UC N/A1.4 57.3 2.77 0.87 0.32  86 32 Ex 4 25:75 UC N/A 0.5 57.3 1.22 0.38 NA 87 32 Ex 4 25:75 150 4 0.1 38.2 6.11 2.87 0.38  88 32 Ex 4 25:75 250 40.4 57.3 2.67 0.83 0.32  89 32 Ex 4 25:75 250 4 0.3 57.3 2.1 0.65 NA  9032 Ex 4 25:75 250 4 0.2 57.3 5.5 1.70 0.38  91 32 Ex 4 25:75 250 4 0.157.3 6.84 2.10 0.40  92 32 Ex 4 25:75 500 4 0.4 57.3 5.97 1.87 0.35  9332 Ex 3 25:75 800 4 1.2 95.4 0 0.00 NA  94C Ex 1, PtG Comp Ex 4 0:1 UCN/A 0.5 57.3 2.92 0.91 0.31  95C Comp Ex 4 Comp Ex 4 0:1 UC N/A 1.2 57.30 0 NA **96C Comp Ex 5 Comp Ex 5 80:20 UC N/A 0.8 57.3 3.94 1.20 0.36**97C   39C Comp Ex 2 0:1 250 4 0 57.3 0.26 0.08 NA  98C   40C Comp Ex 61:0 UC N/A 1 57.3 3.62 1.13 0.30  99C   40C Comp Ex 6 1:0 250 4 0.5 57.34.21 1.32 0.37  100C   40C Comp Ex 6 1:0 250 4 0.3 57.3 3.55 1.11 0.38 101 33 Ex 3 80:20 250 4 0 57.3 9.98 3.12 0.43  102 33 Ex 3 80:20 250 40.3 57.3 11.05 3.45 0.41  103 34 Ex 3 50:50 250 4 0 57.3 14.69 4.59 0.41 104 34 Ex 3 50:50 250 4 0 38.2 8.11 3.81 0.37  105* 36 Ex 5 65:35 250 40 57.3 5.89 1.84  .37  106* 37 Ex 5 65:35 250 4 0 57.3 7.74 2.44  .37 107 33 Ex 9 80:20 250 4 0 57.3 9.47 2.98  .43 UC = uncalcined N/A - notapplicable *= Tray Dried **= Non-Agglomerated physical blend

TABLE X Clay (Wt. % in Polymer Particle Size Distribution (Microns)Support- 0-75 75-150 150-250 250-500 500-850 850-2000 >2000 Run No.Activator) (Wt. %) (Wt. %) (Wt. %) (Wt. %) (Wt. %) (Wt. %) (Wt. %) +45*20 0 0 0 12.3 70 17.2 0.1  56* 20 0 0 0 14.4 80 4.2 0  67* 35 0 0 0 2.629 68.9 0  94C 100  7.0 19.6 23.4 31.2 11.4 3.8 7.2  96C*** 20 7.7 32.334 15 7.3 4.5 2 105** 35 3.2 4.8 8 24.2 41.5 18.2 0 106** 35 4.5 5.8 8.723.5 37.2 20.4 0 *= Spray Dried **= Tray Dried ***= Physical Mixture +=Polymer has Mw = 348,200, Mn = 34,700 and Mw/Mn = 10.0

TABLE XI AlBu₃ (mmol/g) 1.2 Fe = 38.2 Fe = 52.3 μmol Fe = 76.3 μmol Fe =95.4 μmol μmol 150° C. 500° C. 800° C. RT 0.8 Fe = 52.3 Fe = 38.2 μmolFe = 95.4 μmol Fe = 76.3 μmol μmol 500° C. 150° C. RT 800° C. 0.4 Fe =76.3 Fe = 95.4 μmol Fe = 38.2 μmol Fe = 52.3 μmol μmol RT 800° C. 500°C. 150° C. 0.1 Fe = 95.4 Fe = 76.3 μmol Fe = 52.3 μmol Fe = 38.2 μmolμmol 800° C. RT 150° C. 500° C. 20% Clay 35% Clay 50% Clay 75% Clay

The principles, preferred embodiments, and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected herein, however, is notto be construed as limited to the particular forms disclosed, sincethese are to be regarded as illustrative rather than restrictive.Variations and changes may be made by those skilled in the art, withoutdeparting from the spirit of the invention.

What is claimed is:
 1. A coordinating catalyst system capable ofpolymerizing olefins comprising: (I) as a pre-catalyst, at least onenon-metallocene, non-constrained geometry, bidentate ligand containingtransition metal compound or tridentate ligand containing transitionmetal compound capable of (A) being activated upon contact with thecatalyst support-activator agglomerate of (II) or (B) being converted,upon contact with an organometallic compound, to an intermediate capableof being activated upon contact with the catalyst support-activatoragglomerate of (II), wherein the transition metal is at least one memberselected from Groups 3 to 10 of the Periodic table; in intimate contactwith (II) catalyst support-activator agglomerate comprising a compositeof (A) at least one inorganic oxide component selected from SiO₂, Al₂O₃,MgO, AlPO₄, TiO₂, ZrO₂, and Cr₂O₃ and (B) at least one ion containinglayered material having interspaces between the layers and sufficientLewis acidity, when present within the catalyst support-activatoragglomerate, to activate the pre-catalyst when the pre-catalyst is incontact with the catalyst support-activator agglomerate, said layeredmaterial having a cationic component and an anionic component, whereinsaid cationic component is present within the interspaces of the layeredmaterial, said layered material being intimately associated with saidinorganic oxide component within the agglomerate in an amount sufficientto improve the activity of the coordinating catalyst system forpolymerizing ethylene monomer, expressed as Kg of polyethylene per gramof catalyst system per hour, relative to the activity of a correspondingcatalyst system employing the same pre-catalyst but in the absence ofeither Component A or B of the catalyst support-activator agglomerate;wherein the amounts of the pre-catalyst and catalyst support-activatoragglomerate which are in intimate contact are sufficient to provide aratio of micromoles of pre-catalyst to grams of catalystsupport-activator agglomerate of from about 5:1 to about 500:1.
 2. Thecatalyst system of claim 1 which additionally comprises as a thirdcomponent, at least one organometallic compound represented by theformula: M (R¹²)_(s) wherein M represents at least one element of Group1, 2, or 13 of the Periodic Table, tin or zinc, and each R¹²independently represents at least one of hydrogen, halogen, orhydrocarbon-based group, and “s” is a number corresponding to theoxidation number of M; said organometallic compound being in intimatecontact with said pre-catalyst in an amount sufficient to provide amolar ratio of organometallic compound to pre-catalyst from about0.001:1 to about 10,000:1.
 3. The catalyst system of claim 1 wherein thepre-catalyst is a bidentate ligand containing transition metal compound

represented by the formula: wherein: (I) each A independently representsoxygen, sulfur, phosphorus or nitrogen; (II) Z represents a transitionmetal selected from at least one of the group of Fe, Co, Ni, Ru, Rh, Pd,Os, Ir and Pt in the +2 oxidation state, and Ti, V, Cr, Mn, Zr, and Hfin the +2, +3 or +4 oxidation state; (III) each L and L′ independentlyrepresents a ligand group selected from at least one of hydrogen,halogen, hydrocarbon based radical, or two L groups, together representa hydrocarbon based radical, which, together with Z, constitute aheterocyclic ring structure; and (IV) “a” is an integer of 0 or 1 andrepresents the number of L′ groups bound to Z, the line joining A to theother A represents hydrocarbon based radicals joined to A by a double orsingle bond, and the lines joining each A to Z represent a covalent ordative bond.
 4. The catalyst system of claim 1 wherein the transitionmetal compound is a tridentate ligand containing transition metalcompound represented by the formula:

wherein: (V) each A independently represents oxygen, sulfur, phosphorousor nitrogen; (VI) Z represents a transition metal selected from at leastone of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2oxidation state and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4oxidation state; (VII) each L and L′ independently represents a ligandgroup selected from at least one of hydrogen, halogen and hydrocarbonbased radical, or two L groups together represent a hydrocarbon basedradical, which together with Z, constitute a heterocyclic ringstructure; and (VIII) “a” is an integer of 0, 1, or 2 and represents thenumber of L′ groups bound to Z, the lines joining each A to each other Arepresent hydrocarbon based radicals joined to A by a double or singlebond, and the lines joining each A to Z represent a covalent or dativebond.
 5. The catalyst system of any one of claims 3 and 4 wherein each Arepresents a nitrogen atom, each L and L′ is independently selected fromhalogen, hydrocarbyl and mixtures thereof, or two L groups togetherrepresent hydrocarbylene which together with Z constitute a 3 to 7membered heterocyclic ring structure.
 6. The catalyst system of any oneof claims 3 and 4 wherein at least one L of the pre-catalyst ishydrocarbyl.
 7. The catalyst system of claim 6 wherein Z is at least oneof Ni, Pd, Fe or Co.
 8. The catalyst system of claim 3 wherein Z is atleast one of Ni or Pd and each L is independently at least one ofchlorine, bromine, iodine, or C₁-C₈ alkyl.
 9. The catalyst system ofclaim 4 wherein Z is at least one of iron or cobalt and each L isindependently at least one of chlorine, bromine, iodine, or C₁-C₈ alkyl.10. The catalyst system of any one of claims 3 and 4 wherein L is atleast one of halogen or hydrogen, and the catalyst system furthercomprises at least one organometallic compound represented by theformula: M(R¹²)_(s) wherein M is aluminum, R¹² is a hydrocarbon basedgroup, and “s” is 3, intimately associated with the pre-catalyst in anamount sufficient to provide a molar ratio of organometallic compound totransition metal in the pre-catalyst of from about 0.001:1 to about250:1.
 11. The catalyst system of claim 1 wherein the layered materialof the catalyst support-activator agglomerate is at least one of clay orclay minerals having a negative charge of below
 0. 12. The catalystsystem of claim 11 wherein the layered material is a smectite clay, theweight ratio of inorganic oxide to clay in the catalystsupport-activator agglomerate is from about 0.25:1 to about 99:1, andthe ratio of micromoles of pre-catalyst to grams of catalystsupport-activator agglomerate is from about 10:1 to about 250:1.
 13. Thecatalyst system of claim 12 wherein the smectite clay is at least one ofmontmorillonite and hectorite, the weight ratio of inorganic oxide toclay in the catalyst support-activator agglomerate is from about 0.5:1to about 20:1, and the ratio of micromoles of pre-catalyst to grams ofcatalyst support-activator agglomerate is from about 30:1 to about100:1.
 14. The catalyst system of claim 1 wherein the inorganic oxidecomponent is SiO₂, the weight ratio of SiO₂ to layered material in thecatalyst support-activator agglomerate is from about 1:1 to about 10:1,and the ratio of micromoles of pre-catalyst to grams of catalystsupport-activator agglomerate is from about 80:1 to about 100:1.
 15. Thecatalyst system of anyone of claims 1 and 2 wherein the catalystsupport-activator agglomerate comprises spray dried agglomerateparticles comprising constituent particles of at least one of saidinorganic oxides and at least one of said layered materials wherein: (I)at least 80% of the volume of the agglomerated particles smaller thanD₉₀ of the entire agglomerate particle size distribution possesses amicrospheroidal morphology; (II) the catalyst support-activatoragglomerate particles possess: (A) an average particle size of fromabout 4 to about 250 microns, and (B) a surface area of from 20 to about800 m²/gm; and (III) the constituent inorganic oxide particles fromwhich the agglomerate particles are derived have an average particlesize, prior to spray drying, of from about 2 to about 10 microns, andthe constituent layered material particles have an average particlesize, prior to spray drying, of from about 0.01 to about 50 microns. 16.The catalyst system of claim 15 wherein the constituent inorganic oxideparticles from which the agglomerate particles are derived, prior tospray drying, have: (I) an average particle size of from about 4 toabout 9 microns, (II) a particle size Distribution Span of from about0.5 to about 3.0 microns, and (III) a colloidal particle size content offrom about 2 to about 60 wt. %, based on the constituent inorganic oxideparticle weight.
 17. A coordinating catalyst system formed by theprocess comprising: (I) agglomerating to form a catalystsupport-activator agglomerate: (A) at least one inorganic oxidecomponent comprising SiO₂, Al₂O₃, MgO, AlPO₄, TiO₂, ZrO₂, or Cr₂O₃ with(B) at least one ion containing layered material having interspacesbetween the layers and sufficient Lewis acidity, when present within thecatalyst support-activator agglomerate, to activate the transition metalof the pre-catalyst of 11 when the pre-catalyst is in contact with thecatalyst support-activator agglomerate, said layered material having acationic component and an anionic component, wherein said cationiccomponent is present within the interspaces of the layered material,said layered material being intimately associated with said inorganicoxide component within said catalyst support-activator agglomerate in anamount sufficient to improve the activity of the coordinating catalystsystem for polymerizing ethylene monomer, expressed as Kg ofpolyethylene per gram of catalyst system per hour, relative to theactivity of a corresponding catalyst system employing the samepre-catalyst but in the absence of either Component A or B of thecatalyst support-activator agglomerate; (II) providing as apre-catalyst, at least one non-metallocene, non-constrained geometry,transition metal compound selected from bidentate ligand containingtransition metal compound, and tridentate ligand containing transitionmetal compound capable of (A) being activated upon contact with thecatalyst support-activator agglomerate of (I), or (B) being converted,upon contact with an organometallic compound, to an intermediate capableof being activated upon contact with the catalyst support-activatoragglomerate of I, wherein the transition metal is at least one elementselected from Groups 3 to 10 of the Periodic Table; (III) contacting thecatalyst support-activator agglomerate and pre-catalyst in the presenceof at least one inert liquid hydrocarbon in a manner sufficient toprovide a ratio of micromoles of pre-catalyst to grams ofsupport-activator of from about 5:1 to about 500:1.
 18. The catalystsystem of claim 17 prepared by the additional step of including at leastone organometallic compound in the liquid hydrocarbon of step III, saidorganometallic compound being represented by the formula: M (R¹²)_(s)wherein M represents at least one element of Groups 1, 2, or 13 of thePeriodic Table, tin or zinc, and each R¹² independently represents atleast one of hydrogen, halogen, or hydrocarbon-based group, and “s” is anumber corresponding to the oxidation number of M, said organometalliccompound being in intimate contact with said pre-catalyst, wherein theamount of organometallic compound present is sufficient to provide amolar ratio of organometallic compound to pre-catalyst of from about0.001:1 to about 250:1.
 19. The catalyst system of claim 17 wherein thetransition metal compound is a bidentate ligand containing transitionmetal compound represented by the formula:

wherein: (I) each A independently represents oxygen, sulfur, phosphorusor nitrogen; (II) Z represents a transition metal selected from at leastone of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2oxidation state, and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4oxidation state; (III) each L and L′ independently represents a ligandgroup selected from at least one of hydrogen, halogen, and hydrocarbonbased radical, or two L groups together represent a hydrocarbon basedradical which, together with Z, constitute a heterocyclic ringstructure; and (IV) “a” is an integer of 0 or 1 and represents thenumber of L′ groups bound to Z, the line joining A to the other Arepresents hydrocarbon based radicals joined to A by a double or singlebond, and the lines joining each A to Z represent a covalent or dativebond.
 20. The catalyst system of claim 17 wherein the transition metalcompound is a tridentate ligand containing transition metal compoundrepresented by the formula:

wherein: (I) each A independently represents oxygen, sulfur, phosphorousor nitrogen; (II) Z represents a transition metal selected from at leastone member of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the+2 oxidation state and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4oxidation state; (III) each L and L′ independently represents a ligandgroup selected from at least one of hydrogen, halogen, and hydrocarbonbased radical, or two L groups together represent a hydrocarbon basedradical which, together with Z, constitute a heterocyclic ringstructure; and (IV) “a” is an integer of 0, 1 or 2 and represents thenumber of L′ groups bound to Z, the lines joining each A to each other Arepresent hydrocarbon based radicals joined to A by a double or singlebond, and the lines joining each A to Z represent a covalent or dativebond.
 21. The catalyst system of any one of claims 19 and 20 whereineach A represents nitrogen, each L and L′ is independently halogen,hydrocarbyl, or mixtures thereof, or two of said L groups togetherrepresent a hydrocarbylene group which, together with Z, constitute a 3to 7 membered heterocyclic ring structure.
 22. The catalyst system ofclaim 21 wherein M is aluminum, “s” is 3, and R¹² is C₁ to C₂₄ alkyl,and each L of the pre-catalyst is halogen.
 23. The catalyst compositionof any one of claims 19 and 20 wherein at least one L of thepre-catalyst is hydrocarbyl.
 24. The catalyst system of any one ofclaims 19 and 20 wherein Z is at least one of Ni, Pd, Fe, or Co.
 25. Thecatalyst system of claim 19 wherein Z is at least one of Ni or Pd andeach L is independently selected from chlorine, bromine, iodine, orC₁-C₈ alkyl.
 26. The catalyst system of claim 20 wherein Z is at leastone of iron or cobalt and each L is independently selected fromchlorine, bromine, iodine, or C₁-C₈ alkyl.
 27. The catalyst system ofclaim 19 prepared by the additional step of including in the inerthydrocarbon liquid of step III, at least one organometallic compoundrepresented by the formula: M (R¹²)_(s) wherein M represents at leastone element of Group 1, 2, or 13 of the Periodic Table, tin or zinc, andeach R¹² independently represents at least one of hydrogen, halogen, orhydrocarbyl group, and “s” is the oxidation number of M; saidorganometallic compound being in intimate contact with said pre-catalystin an amount sufficient to provide a molar ratio of organometalliccompound to pre-catalyst of from about 0.01:1 to about 125:1.
 28. Thecatalyst system of claim 20 prepared by the additional steps ofincluding in the inert hydrocarbon liquid of step III, at least oneorganometallic compound represented by the formula: M (R¹²)_(s) whereinM represents at least one element of Group 1, 2, or 13 of the PeriodicTable, tin or zinc, and each R¹² independently represents at least oneof hydrogen, halogen, or hydrocarbyl group, and “s” is the oxidationnumber of M; said organometallic compound being in intimate contact withsaid pre-catalyst in an amount sufficient to provide a molar ratio oforganometallic compound to pre-catalyst of from about 0.1:1 to about10:1.
 29. The catalyst system of claim 27 wherein M is aluminum, R¹² isalkyl or alkoxy, “s” is 3, Z is at least one of Ni or Pd, and L ishalogen.
 30. The catalyst system of claim 28 wherein M is aluminum, R¹²is alkyl or alkoxy, “s” is 3, Z is selected from at least one of Fe orCo, and L is halogen.
 31. The catalyst system of claim 17 wherein theion containing layered material is at least one of clay or clay mineralhaving a negative charge below
 0. 32. The catalyst system of claim 31wherein the layered material is a smectite clay, the weight ratio ofinorganic oxide to clay in the catalyst support-activator agglomerate isfrom about 0.25:1 to about 99:1, and the ratio of micromoles ofpre-catalyst to grams of catalyst support-activator agglomerate is fromabout 10:1 to about 250:1.
 33. The catalyst system of claim 32 whereinthe smectite clay is at least one of montmorillonite or hectorite, theweight ratio of inorganic oxide to clay in the catalystsupport-activator agglomerate is from about 0.5:1 to about 20:1, and theratio of micromoles of pre-catalyst to grams of catalystsupport-activator agglomerate is from about 30:1 to about 100:1.
 34. Thecatalyst system of claim 17 wherein the inorganic oxide component isSiO₂, the weight ratio of SiO₂ to layered material in the catalystsupport-activator agglomerate is from about 1:1 to about 10:1, and theratio of micromoles of pre-catalyst to grams of catalystsupport-activator agglomerate is from about 80:1 to about 100:1.
 35. Thecatalyst system of any one of claims 17 and 18 wherein the catalystsupport-activator agglomerate comprises spray dried agglomerateparticles comprising constituent particles of at least one of saidinorganic oxides and at least one of said layered materials wherein: (I)at least 80% of the volume of the agglomerated particles smaller thanD₉₀ of the entire agglomerate particle size distribution possesses amicrospheroidal morphology; (II) the catalyst support-activatoragglomerate particles possess: (A) an average particle size of fromabout 4 to about 250 microns, and (B) a surface area of from 20 to about800 m²/gm; (III) the constituent inorganic oxide particles from whichthe agglomerate particles are derived have an average particle size,prior to spray drying, of from about 2 to about 10 microns, and theconstituent layered material particles have an average particle size,prior to spray drying, of from about 0.01 to about 50 microns.
 36. Thecatalyst system of claim 35 wherein the constituent inorganic oxideparticles from which the agglomerate particles are derived, prior tospray drying, have: (I) an average particle size of from about 4 toabout 9 microns, (II) a particle size Distribution Span of from about0.5 to about 3.0 microns, and (III) and a colloidal particle sizecontent of from about 2 to about 60 wt. %, based on the constituentinorganic oxide particle weight.
 37. A process for preparing a catalystsystem for polymerizing olefins, said process comprising: (I)agglomerating to form a catalyst support-activator agglomerate: (A) atleast one inorganic oxide component comprising SiO₂, Al₂O₃, MgO, AlPO₄,TiO₂, ZrO₂, or Cr₂O₃ with (B) at least one ion containing layeredmaterial having interspaces between the layers and sufficient Lewisacidity, when present within the catalyst support-activator agglomerate,to activate the pre-catalyst compound of (II) when the pre-catalyst isin contact with the catalyst support-activator agglomerate, said layeredmaterial having a cationic component and an anionic component, whereinsaid cationic component is present within the interspaces of the layeredmaterial, said layered material being intimately associated with saidinorganic oxide component within the agglomerate in amounts sufficientto improve the activity of the coordinating catalyst system forpolymerizing ethylene monomer, expressed as Kg of polyethylene per gramof catalyst system per hour, relative to the activity of a correspondingcatalyst system employing the same pre-catalyst but in the absence ofeither Component A or B of the catalyst support-activator agglomerate;(II) providing as a pre-catalyst, at least one non-metallocene,non-constrained geometry transition metal compound selected frombidentate ligand containing transition metal compound and tridentateligand containing transition metal compound capable of (A) beingactivated upon contact with the catalyst support-activator agglomerate,or (B) being converted, upon contact with an organometallic compound, toan intermediate capable of being activated upon contact with thecatalyst support-activator agglomerate, wherein the transition metal isat least one member selected from Groups 3 to 10 of the Periodic Table;(III) contacting the catalyst support-activator agglomerate andpre-catalyst in the presence of at least one inert liquid hydrocarbon ina manner sufficient to provide in the liquid hydrocarbon, a ratio ofmicromoles of pre-catalyst to grams of catalyst support-activatoragglomerate of from about 5:1 or to about 500:1, and to cause at leastone of absorption and adsorption of the pre-catalyst by the catalystsupport-activator agglomerate.
 38. The process of claim 37 furthercomprising including at least one organometallic compound in the inertliquid hydrocarbon of step III represented by the formula: M (R¹²)_(s)wherein M represents at least one element of Groups 1, 2, or 13 of thePeriodic Table, tin or zinc, and each R¹² independently represents atleast one of hydrogen, halogen, or hydrocarbon-based group, and “s” isthe oxidation number of M, said organometallic compound being inintimate contact with said pre-catalyst, wherein the amount oforganometallic compound present in the liquid hydrocarbon is sufficientto provide a molar ratio of organometallic compound to pre-catalyst offrom about 0.001:1 to about 250:1.
 39. The process of claim 37 whereinthe transition metal compound is a bidentate ligand containingtransition metal

compound represented by the formula: wherein: (I) each A independentlyrepresents oxygen, sulfur, phosphorus, or nitrogen; (II) Z represents atransition metal selected from at least one of the group of Fe, Co, Ni,Ru, Rh, Pd, Os, Ir and Pt in the +2 oxidation state, and Ti, V, Cr, Mn,Zr, and Hf in the +2, +3 or +4 oxidation state; (III) each L and L′independently represents a ligand group selected from at least one ofhydrogen, halogen, and hydrocarbon based radical, or two L groupstogether represent a hydrocarbon based radical, which together with Z,constitute a heterocyclic ring structure; and (IV) “a” is an integer of0 or 1 and represents the number of L′ groups bound to Z, the linejoining A to the other A represents hydrocarbon based radicals joined toA by a double or single bond, and the lines joining each A to Zrepresent a covalent or dative bond.
 40. The process of claim 37 whereinthe transition metal compound is a tridentate ligand containingtransition metal compound represented by the formula:

wherein: (I) each A independently represents oxygen, sulfur, phosphorousor nitrogen; (II) Z represents a transition metal selected from at leastone of the group of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt in the +2oxidation state and Ti, V, Cr, Mn, Zr, and Hf in the +2, +3 or +4oxidation state; (III) each L and L′ independently represents a ligandgroup selected from at least one of hydrogen, halogen, and hydrocarbonbased radical, or two L groups together represent a hydrocarbon basedradical which, together with Z, constitute a heterocyclic ringstructure; and (IV) “a” is an integer of 0, 1 or 2 and represents thenumber of L′ groups bound to Z, the lines joining each A to each other Arepresent hydrocarbon based radicals joined to A by a double or singlebond, and the lines joining each A to Z represent a covalent or dativebond.
 41. The process of any one of claims 39 and 40 wherein each Arepresents nitrogen, each L and L′ is independently selected fromhalogen, hydrocarbyl and mixtures thereof, or two of said L groupstogether represent a hydrocarbylene group which, together with Z,constitute a 3 to 7 membered heterocyclic ring structure.
 42. Theprocess of claim 38 wherein M is aluminum, “s” is 3, and R¹² is C₁ toC₂₄ alkyl, and each L of the pre-catalyst is halogen.
 43. The process ofclaims 39 and 40 wherein at least one L of the pre-catalyst ishydrocarbyl.
 44. The process of any one of claims 39 and 40 wherein Z isat least one of Ni, Pd, Fe, or Co.
 45. The process of claim 39 wherein Zis selected from at least one of Ni or Pd and each L is independentlyselected from chlorine, bromine, iodine, and C₁-C₈ alkyl.
 46. Theprocess of claim 40 wherein Z is at least one of iron or cobalt and eachL is independently selected from chlorine, bromine, iodine, or C₁-C₈alkyl.
 47. The process of claim 39 comprising the additional step ofincluding in the inert liquid hydrocarbon of step III, at least oneorganometallic compound represented by the formula: M (R¹²)_(s) whereinM represents at least one element of Group 1, 2, or 13 of the PeriodicTable, tin or zinc, and each R¹² independently represents at least oneof hydrogen, halogen, and hydrocarbon based group, and “s” is theoxidation number of M; said organometallic compound being in intimatecontact with said pre-catalyst in an amount sufficient to provide amolar ratio of pre-catalyst to organometallic compound from about 0.01:1to about 125:1.
 48. The process of claim 40 comprising the additionalstep of including at least one organometallic compound in the inertliquid hydrocarbon of step III represented by the formula: M (R¹²)_(s)wherein M represents at least one element of Group 1, 2, or 13 of thePeriodic Table, tin or zinc, and each R¹² independently represents atleast one of hydrogen, halogen and hydrocarbon based group, and “s” isthe oxidation number of M; said organometallic compound being inintimate contact with said pre-catalyst in an amount sufficient toprovide a molar ratio of pre-catalyst to organometallic compound in thehydrocarbon liquid from about 0.1:1 to about 10:1.
 49. The process ofclaim 47 wherein M is aluminum, R¹² is alkyl or alkoxy, “s” is 3, Z isselected from at least one of Ni or Pd, and L is halogen.
 50. Theprocess of claim 48 wherein M is aluminum, R¹² is alkyl or alkoxy, “s”is 3, Z is selected from at least one of Fe or Co, and L is halogen. 51.The process of claim 37 wherein the ion containing layered material isat least one of clay or clay mineral having a negative charge below 0.52. The process of claim 51 wherein the layered material is a smectiteclay, the weight ratio of inorganic oxide to clay in the catalystsupport activator agglomerate is from about 0.25:1 to about 99:1, andthe ratio of micromoles of pre-catalyst to grams of catalystsupport-activator agglomerate is from about 10:1 to about 250:1.
 53. Theprocess of claim 52 wherein the smectite clay is at least one ofmontmorillonite and hectorite, the weight ratio of inorganic oxide toclay in the catalyst support-activator agglomerate is from about 0.5:1to about 20:1, and the ratio of micromoles of transition metal in thepre-catalyst to grams of catalyst support-activator agglomerate is fromabout 30:1 to about 100:1.
 54. The process of claim 37 wherein theinorganic oxide is SiO₂, the weight ratio of SiO₂ to layered material inthe catalyst support-activator agglomerate is from about 1:1 to about10:1, and the ratio of micromoles of pre-catalyst to grams of catalystsupport-activator agglomerate is from about 30:1 to about 100:1.
 55. Theprocess of any one of claims 37 and 38 wherein the catalystsupport-activator agglomerate comprises spray dried agglomerateparticles comprising constituent particles of at least one of saidinorganic oxides and at least one of said layered materials wherein: (I)at least 80% of the volume of the agglomerated particles smaller thanD₉₀ of the entire agglomerate particle size distribution possesses amicrospheroidal morphology; (II) the catalyst support-activatoragglomerate particles possess (A) an average particle size of from about5 to about 250 microns, and (B) a surface area of from 20 to about 800m²/gm; (III) the constituent inorganic oxide particles from which theagglomerate particles are derived have an average particle size, priorto spray drying, of from about 2 to about 10 microns and the constituentlayered material particles have an average particle size, prior to spraydrying, of from about 0.01 to about 50 microns.
 56. The process of claim55 wherein the constituent inorganic oxide particles from which thecatalyst support-activator agglomerate particles are derived, prior tospray drying, have: (I) an average particle size of from about 4 toabout 9 microns; (II) a particle size Distribution Span of from about0.5 to about 3.0 microns; and (III) a colloidal particle size content offrom about 2 to about 60 wt. %, based on the constituent inorganic oxideweight.
 57. The process of claim 37 wherein the catalystsupport-activator agglomerate and pre-catalyst are agitated in theliquid hydrocarbon at a temperature of from about 0 to about 80° C. fora period of from about 0.5 to about 1440 minutes.
 58. The process ofclaim 37 wherein the liquid hydrocarbon of step III is separated fromthe mixture of catalyst support-activator agglomerate and pre-catalyst.59. The process of claim 38 wherein the liquid hydrocarbon of step IIIis separated from the mixture of catalyst support-activator agglomerate,pre-catalyst and organometallic compound.
 60. The process of claim 38wherein the organometallic compound is contacted with pre-catalyst priorto contract with the catalyst support-activator agglomerate.
 61. Theprocess of claim 37 further comprising including in the inert liquidhydrocarbon of step III, at least one organometallic compoundrepresented by the formula: M (R¹²)_(s) wherein M represents at leastone element of Groups 1, 2, or 13 of the Periodic Table, tin or zinc,and each R¹² independently represents at least one of hydrogen, halogen,and hydrocarbyl group, and “s” is the oxidation number of M, saidorganometallic compound being in intimate contact with saidpre-catalyst, wherein the amount of organometallic compound present issufficient to provide a ratio of millimoles of organometallic compoundto grams of catalyst support-activator agglomerate of from about 0.001:1to about 2:1.
 62. The process of claim 61 wherein said ratio oforganometallic compound to support activator is from about 0.1:1 toabout 0.8:1.
 63. The process of claim 37 further comprising calciningthe catalyst support-activator agglomerate formed in step I at atemperature of from about 100 to about 800° C. for a period of fromabout 1 to about 600 minutes prior to step III.
 64. The process of claim37 further comprising recovering the support-activator having thepre-catalyst impregnated therein from the liquid hydrocarbon.